For the better teaching of architecture, sculpture and the other arts, the Academy initiated by Parini was provided with a collection of casts after the Antique, an essential for inculcating a refined Neoclassicism in the students.

Under Parini's successors, the abate Carlo Bianconi (1778–1802) and artist Giuseppe Bossi (1802–1807), the Academy acquired the first paintings of its Pinacoteca during the reassignment of works of Italian art that characterized the Napoleonic era.

Raphael's Sposalizio (the Marriage of the Virgin) was the key painting of the early collection, and the Academy increased its cultural scope by taking on associates across the First French Empire: David, Pietro Benvenuti, Vincenzo Camuccini, Canova, Thorvaldsen and the archaeologist Ennio Quirino Visconti.

In 1805, under Bossi's direction, the series of annual exhibitions was initiated with a system of prizes, a counterpart of the Paris Salons, which served to identify Milan as the cultural capital for contemporary painting in Italy through the 19th century.

The Academy's artistic committee, the Commissione di Ornato exercised a controlling influence on public monuments, a precursor of today's Sopraintendenze Delle Belle Arti.