At the start of the 19th century, several medieval buildings (notably the refectory) were demolished and in their place Viollet-le-Duc and his pupil Darcy put up new exhibition galleries, accessed by a Gothic Revival monumental stair offering an interplay of richly complicated vaulting systems.

The archaeologist Alexandre Du Mège occupied the cloister and rebuilt it to be able to house the medieval collections gathered from Toulouse's destroyed religious buildings such as the basilique Saint-Sernin.

[4] The progressive concern of the museum's founder Jean-Antoine Chaptal, an early example of cultural devolution, was intended to ensure that "each collection presents an interesting series of paintings representing all the masters, all the genres and all the schools".

The Italian holdings span from the 14th to the 18th century with works by Neri di Bicci, Lorenzo Monaco, Pietro Perugino, Jacopo Zucchi, Guido Reni, Guercino, Bernardo Strozzi, Baciccio, Carlo Maratta, Crespi, Francesco Solimena, Guardi.

It is particularly strong in 12th-century Romanesque sculpture from the city's three main religious buildings - the priory of Notre-Dame de la Daurade, the basilica of Saint-Sernin and the cathedral of Saint-Étienne.