[2][3] The library was founded at the end of the 18th century in the Palazzo degli Studi (which now houses the Museo Archeologico), with its nucleus formed of books holdings of the Palazzo Capodimonte, the library from the celebrated Farnese Collection that Carlo di Borbone had transferred to Naples in 1734).

Opened to the public in 1804 under the name of the Reale Biblioteca di Napoli, and directed by the great humanist Juan Andrés, who composed his most important memoir, in Latin, published in Madrid by the Instituto Juan Andrés de Comparatística y Globalización with a study that broadens and renews the knowledge of this key and very intricate place in European culture.

After long debate and on the suggestion and efforts of Benedetto Croce, in 1922 the library was moved to its present location at Palazzo Reale, granted to the library by King Victor Emmanuel III (whose name it still bears).

After the transfer, the collections of other important Neapolitan libraries were annexed to it, including the Biblioteca Brancacciana (formed in Rome by Cardinal Francesco Maria Brancaccio in the first half of the 17th century, transferred to Naples, and finally becoming Naples' first public library).

It suffered during the Second World War due to the German and Allied occupations of Naples (being set fire to by the Germans in the four days of Naples), though the most precious manuscripts had been transferred to safer locations and remained there until the library reopened in 1945.