du Pont's personal life is well documented by the photographic collection he left, and it followed certain themes. The greatest of these may be horticultural interests which developed during his creation of the celebrated Longwood Gardens in Kennett Square, Pennsylvania, where he lived. du Pont made many foreign and domestic journeys and recorded his travels. His large extended family is included in this collection.

This collection is organized into seven series: Longwood Gardens; Individuals and families; Groups and organizations; E.I. du Pont de Nemours & Company; Trips and vacations; Places; and Culture, society, and service. It should be noted that du Pont, especially in his younger years, was interested in photography, and his own work is included in the collection.

The Longwood Gardens series documents the creation and expansion of Longwood Gardens. The photographs of the property are arranged chronologically. They start with a few nineteenth century views of the property when it was the property of the Peirce family who owned it through the legacy of a William Penn land grant and continue through its intensive development under the direction of du Pont who gave personal attention to building fountains, conservatories, and a popular outdoor theater. Though the du Pont’s hosted an annual garden party, there are only images of one garden party from 1915. There are two albums of Longwood Gardens, one dates from 1907 through 1913 and shows the construction of a dam, tree plantings, the formal garden, fountains, and the Peirce-du Pont house renovation. The second album is of photographs by Gould White and dates to the 1920s. The album contains some hand-colored images by M.M. Pugh, particularly of the fountains. There are several sets of postcards that date as early as 1909 through 1931, the largest set of postcards are from 1928. Most of the postcards are black and white, though some are in color. There are glass plate negatives of the gardens and grounds, including the construction of the main conservatory in 1919 and its completion in 1920, as well as images of the mansion, and a set of images of a group of people digging out a snow drift. There are glass stereoview autochromes of the conservatory, gardens, and grounds from around 1922 and 1928, as well as color glass lantern slides of the conservatory in 1924 and garden views in 1937. There are two sets of Dufaycolor glass transparencies of garden views, grounds, and the mansion dating from around 1935-1936. There are also several issues of the newsletters Longwood Chimes and Longwood Gardens Employees, which date from 1985 through 1991.

The Individuals and families series includes includes du Pont, his family and extended family, friends and associates. The images are mostly individual portraits of identified people, over half of this series contains photographs of various du Pont family members, with particular emphasis on P.S. du Pont. There are group portraits and snapshots of families, many identified, but not always. Most of the photographs are original and there are a few original engravings, however, there are also many photographic reproductions of engravings, paintings, or drawings of those who lived prior to the invention of photography in 1826. There are glass and film negatives taken by P.S. du Pont himself. Many of these are from his youth; for example, the 65 negatives taken at Phillips Academy where his brother was a student. There are albums of cartes de visite of which many of the subjects are identified and also an album once in the possession of Henry Algernon du Pont containing Civil War-era military officers (predominantly physicians) and military scenes. There is a two-volume set of du Pont de Nemours family portraits that was printed for the 100 anniversary of the family and an album of the 150th family reunion in 1950. The albums are listed in the beginning of the series, followed by individuals/families listed alphabetically by last name.

The Groups and organizations series consists of some formal and some candids of various regional and national associations, and local informal clubs and societies, as well as photographs of various items and buildings associated with those groups. Half of the series is devoted to the theater troupe of Longwood Gardens, The Brandywiners, with candids of their various plays and portraits of the actors in costume. There are some panoramas including the Third Conference of the Women's Organization for National Prohibition Reform in Washington, the Longwood Fire Company, and the Pennsylvania State Highway Patrol at Longwood Gardens. The series is arranged alphabetically.

The E.I. du Pont de Nemours and Company series contains images of property and buildings, as well as, employees and executives, arranged alphabetically. There are glass negatives documenting the construction of the DuPont Building in Wilmington, Delaware, between 1905 and 1907. There are also photographs from the 150th Anniversary in 1952.

The Trips and vacations series consists of photographs of various du Ponts and acquaintances from their travels around the globe and is organized by person or family. The images are mostly of scenery and candids of the local culture, with some postcards, loose and in albums. Half of this series are photographs from the various trips of P.S. du Pont in South America, Europe, the Caribbean, Mexico, and western and southwestern states in the United States. These photographs date from the early 1900s through 1935.

The Places series is divided into four subseries: Homes, estates, and properties; Delaware/Pennsylvania area; Gardens and parks; and Europe.

The Homes, estates, and properties subseries consists of primarily exterior images of du Pont family homes and other owned properties. There are some images of interiors and non-residential properties. The subseries is listed alphabetically by estate name.

The Delaware/Pennsylvania area subseries includes landscape and city scenes, notable buildings and locations, and roads and is arranged alphabetically. Notably there are images of buildings at Bryn Mawr College dating from 1888 to 1893, presumably from Alice Belin du Pont’s time attending there. There are images of Brandywine scenery in the 1880s through the early 1900s, Wilmington, Delaware landmarks, various area schools, and roads in Unionville, Pennsylvania in the 1920s. There is also a humorous cartoon parodying du Pont family ownership of businesses in Wilmington.

The Gardens and parks subseries consists of images of nature and is arranged alphabetically. There are postcards and photographs from various gardens and parks throughout the United States. There are photographs of beautiful trees and flowers, specifically boxwoods, evergreens, and azaleas. This subseries includes many images of Yellowstone National Park from around the 1900s.

The Europe subseries contains mounted prints of Great Britain and Continental Europe primarily from 1905. Half the subseries relate to France, showing images of significant landmarks and du Pont ancestral estates, in addition to photographs there are engravings, postcards, and drawings. This subseries is arranged alphabetically by country.

The Culture, society, and service series is divided into five subseries: Artwork; Automobiles and machinery; Photography, motion pictures, and audio recordings; Wars and military, and World’s Fairs and amusements.

The Artwork subseries contains both copies and original pieces arranged in alphabetical order. There are three works by Stanley M. Arthurs including The Accolade, American Eagle Ship, and the Landing Governor Printz at Christiana. There are lithographs and watercolors depicting scenes from various operas, a painting of Chateau du Bois in France and a portrait of Marshall Joffre.

The Automobiles and machinery subseries contains pictures of automobiles, farm machinery, and other vehicles. These images date from 1903 to 1932.

The Photography, motion pictures, and audio recordings subseries contains P.S. du Pont’s camera and photography accessories. There are also lantern slides and twelve rolls of motion picture films for the Edison Home Kinetoscope. The lantern slides are of notable landmarks of various countries such as England and Germany and are dated 1912. The films date from 1909 through 1915 and seem to be fictional shorts. There are also several phonograph records, most of the recordings are of band music, two are of speeches by P.S. du Pont on anti-prohibition in 1932, and one is of the Longwood organ in 1950-1952.

The Wars and military subseries is a small amount of materials dating from the 1830s to 1954. Notably there is a set of negatives of the Arrival of the Shoshone in 1919, which brought the last remaining troops home from France in World War I. There are also images related to the Red Cross from World War I.

The World’s Fairs and amusements subseries is primarily images from the 1893 World’s Columbian Exposition. There are rolled unprinted nitrate negatives taken by P.S. du Pont at the World's Columbian Exposition, some of which have been copied and have had contact prints made from the copies, however, there is a set of which that has not been copied or printed. There are also a set of mounted prints from the World’s Columbian Exposition. There is one image of the embalmed body of John Wilkes Booth on exhibit around the 1910s.