The library was founded in 1714 when scholar Antonio Magliabechi bequeathed his entire collection of books, encompassing approximately 30,000 volumes, to the city of Florence.

Since 1935, the collections have been housed in a building designed by Cesare Bazzani and V. Mazzei, located along the Arno River in the quarter of Santa Croce.

A major flood of the Arno River in 1966 damaged nearly one-third of the library's holdings, most notably its periodicals and Palatine and Magliabechi collections.

[1] The Restoration Center was subsequently established and may be credited with saving many of these priceless artifacts.

[2] The library curates the Nuovo soggettario, a "subject indexing tool for various types of resources".