The story of the Library’s book collection links up with the organising in 1819 of the Zoological Cabinet of Warsaw Royal University. Information on that Collection assembled by the Cabinet’s first Custodian, Feliks Paweł Jarocki, makes it likely that books were first and foremost acquired then to make the processing of the Cabinet’s zoological specimens possible. By 1862, Jarocki had accumulated 291 volumes, and this number was increased to 716 during the tenure of his famous successor Władysław Tacznowski. It was at the latter’s initiative, if with financial support on the part of Jan Tadeusz Lubomirski, that the Cabinet’s first publication, Wiadomości z nauk przyrodzonych ("News from the Natural Sciences") was brought out.

The main Book Collection of the National Library of the Natural History Museum derived from the private holdings of the Counts Branicki. The Collection was founded in the 1880s, when the Branickis withdraw their support for the Zoological Cabinet, fearing that whatever had been assembled there would simply be hauled off to Russia. After World War I, Ksawery Branicki felt moved to transfer the entire collection to the Museum, along with what had been intended for the National Museum of Natural History.

Post-1919, the Collection grew rapidly, primarily thanks to a large number of donations from home and abroad, as well as exchanges of publications. This was made possible by the establishment of Museum publications, including Annales Zoologici Musei Zoologici Polonici (1921), Fragmenta Faunistica Musei Polonici Historiae Naturalis (1930) and Acta Ornithologica Musei Zoologici Polonici (1933). As of September 1939, the Library had some 36,718 volumes. Of these around 1500 were lost in the course of World War II, at whose ending (January 1945) the State Zoological Museum and its Library resumed their activities.