Founded by King Charles VII of Naples in 1752, it is one of the oldest art schools in Italy, and offers various levels of study up to and including the equivalent of an Italian laurea (the country's main post-secondary academic degree).

It had been converted from an 18th-century convent attached to the church of San Giovanni Battista delle Monache and was part of a large-scale urban development project led by Alvino and Francesco Saponieri (later Director of the Accademia di Belle Arti).

Jorit, an alumnus, was nominated by Michelina Manzillo and the University Rector Renato Lori to the Wolf Prize 2023 for the arts category.

It began as a collection of paintings, drawings, and sculptures acquired for students to observe and study before beginning work on live models.

In 1891 Filippo Palizzi, who was the president of the academy at the time, proposed housing the collection in a permanent public gallery and building it up to include contemporary art.

The oldest painting is by Jusepe de Ribera (1591 – 1652), but the museum is particularly noted for its collection of 19th-century works including those from the School of Posillipo, many of whose artists had been students and professors at the academy.

In 2007, the museum's Gipsoteca, a collection of plaster casts of important sculptures, like The Thoughtful girl ("Bimba pensosa") by Giovanni De Martino and reliefs, was opened to the public.