The library was formed from the donation of 9000 volumes in 1696 by the jurist and scholar Giovanni Maria Bertolo to the city of Vicenza, with the proviso could become public and provided with a home of "sufficient splendor".

In 1708, after the enlargement of the Palazzo by Francesco Muttoni, the library was opened to the public and entitled "Bertoliana" in honor of its original donor.

During the Second World War, books were hidden initially in Villa Camerini di Montruglio in Mossano and the Praglia Abbey in Teolo.

After the armistice of September 8, 1943, the more valuable of the collections were hidden and walled up in the basement of the Sanctuary of Monte Berico in Verona, or other sites in Venice.

It also contains the donations from 1924 to 1933, by the ambassador Lelio Bonin Longare of the archive and library of the Nievo family, rich in 16th century manuscripts and incunabulum.