Established by the Riccardi family in 1600, the library has been located since 1670 in the Medicean palace on Via Larga, today's Via Cavour, which was sold in that year by the grand-ducal family to the Riccardi. Opened to the public in 1715, enlarged by precious material of humanist nature dating from the 16th century, it became the property first of the State of Tuscany and then of Italy in the early 19th century. For the collection of humanist codexes, autograph texts of scientists and men of letters and for the incunabula kept here, the Riccardian Library was considered almost an appendix of the Laurentian Library, whose administration it shared for many years. Becoming independent in 1942, it was associated with the Morenian Library, established by the scholar Domenico Moreni, thus enlarging the Riccardian's wealth of books dealing with the history, literature and archaeology of Tuscany.

Among the volumes of high scientific and cultural value possessed by the Library is a copy of Pliny's Historia naturalis dating from the 10th century, an edition of Robert Dudley's Arcano del Mare dedicated to Ferdinand II de' Medici and various autograph texts by Pico della Mirandola, Leon Battista Alberti and Agnolo Poliziano.