In the rooms of the main floor is exposed partially the "quadreria" Zambeccari, the ancient collection that the Zambeccari family, important noble family of the Bologna Senate, had assembled during the XVIIIth century in their family Palace near the San Paolo church (now occupied by the Banca Popolare di Milano, in via de’ Carbonesi 11). The collection entered in the Pinacoteca heritage in 1884, after the donation of the Marquess Giacomo Zambeccari that in his last will in 1788 had destinated the collection to the public enjoyment. The collection is compesed by more than 300 artworks and it is the only Bolognese aristocratic collection arrived to us in its entirety.

The pantings' subjects are varius: from religious and mythological scenes, up to still life and genre paintings. A main role is played by paintings of the bolognese and emilian school (almost an half of the collection) but there are even artworks of the Venetian, Genuan, Neapolitan, Tuscany, Lombardy and Roman, such as the Flamish schools.

The display is a reconstruction of that used in the ancient aristocratic collections, where the paintings were placed on the walls in several rows: it is not an exposition that presents the paintings well distanced and in chronological order, but a reproduction of the 1700's taste and style.