The collection brings together portraits of individuals who have shaped the region's history: it includes prints, oil paintings and photographs. The prints alone account for almost 700 items, and there are over 100 paintings.

The series of portraits focuses mainly on likenesses of Neuchâtel's elite: politicians, officials, scientists, literary figures, bankers and traders, artists and writers, intellectuals and philosophers. There are also portraits of prominent foreign figures, mostly French or Prussian rulers. In the photography section, several family collections paint a general picture of the lifestyles of the elite and middle classes.

Good examples include the collections of James De Rutté, Max Bourquin and François Verdier. New acquisitions also focus on portraits of individuals leading everyday lives.