The library was founded in 1714 by Antonio Magliabechi, who donated his collection of 30,000 volumes to the city of Florence. By 1743 it was required that a copy of every work published in Tuscany be submitted to the library.
In 1861 its holdings were combined with those of the Biblioteca Palatina, and since 1870 the library has collected copies of all Italian publications.
Originally the collections were keeped in some rooms of the Uffizi Gallery, but since 1935 the library have been housed in a building designed by Cesare Bazzaniu and V. Mazzei, located along the Arno River in Santa Croce.
Unfortunately, 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. The Restoration Center was subsequently established and saved many of these priceless books. However, much work remains to be done and some items are forever lost.