The Bourbons of Naples personally selected the works to purchase and then had them bound by specialized Neapolitan artisans. Among the royals' personal works were those donated by academics, jurists, and scientists.

The sovereigns periodically held competitions among artisans to award the bindings selected from among the prototypes.

Some volumes in the gallery are part of the Fine Bindings collection of the University Library of Naples, comprising approximately 7,000 works that once belonged to the Bourbon Private Library, as evidenced by the special embossed stamp inside with the three lilies. The Bourbons of Naples personally selected the works to purchase and then had them bound by specialized Neapolitan artisans.

Between 1734 and 1860, numerous bookbinding workshops operated, including the Trani workshop, the most prolific, and Alberto and Enrico Detken, located in the Largo di Palazzo. The others are distributed throughout the historic center of Naples, alternating with the printers' workshops with whom there is a close collaboration. Other significant names among the Kingdom's bookbinders include Giulio Giannini from Rome, Federico Tavel, Pasquale Giannini, Luigi Bianconcini, Pietro Landi, and Luigi Pierallini from Sicily.