The Museum was inaugurated in 1985 for the purpose of documenting the history and evolution of photography from the origins to our own day, as well as conserving the historic heritage of Fratelli Alinari, the world's oldest photography firm still operating today, destined to become famous. Up to 1997 the Museum had its exhibition area, bookshop and photographic archive in Palazzo Rucellai, while the collections had always been kept at the firm's historic seat in Largo Alinari. The exhibition area, moved in October 2006 to the Ex Convento delle Leopoldine, in piazza Santa Maria Novella, contains permanent museum rooms dedicated to the history of Florentine, Italian and worldwide photography; a section on the history of the technique and of cameras; and an educational section for schoolchildren.

The historic collection includes plates on glass, datable between 1852 and 1940, coming from the archives of Alinari, Brogi, Anderson, Chauffourier, Mannelli and Fiorentini. The Vintage Print collection contains vintage and contemporary positive shots from the 19th and 20th centuries, divided into 4 core collections: albums of original vintage photographs; original and contemporary photographic prints; daguerreotypes, ambrotypes and ferrotypes; and various objects pertinent to photography. The collection of negatives consists of negatives coming from photographic studios and amateur photographers, both Italian and foreign, dating from the 19th and 20th centuries, on both plate and film (black-and-white and colour). Lastly, the collection of photographic equipment includes studio and laboratory apparatus: photographic equipment and objectives, technical materials, studio and laboratory instruments, both Italian and foreign, from the very earliest through the second half of the 20th century. Among the core themes, the collection of botanical pictures is noteworthy. The library, continuously enlarged, includes 15,000 titles, among them books on the history of photography from the origins to the present, and documents coming from photographers and photographic archives present in the collections. It is flanked by an art history library containing about 4,500 volumes. The company's administrative archives from 1920 are also found here.