As much as in any other school of painting, portraiture formed a major part of Neo-Impressionist art practice. Portraits of friends, family, patrons and cultural cognoscenti were shown regularly in Neo-Impressionist group exhibitions (although the first two categories were not always clearly identified as such). Neo-Impressionist portraits also featured in broader, 'mixed' exhibitions in which their vibrant Divisionism singled them out. Reviewing the Portraits du Prochain Siècle (Portraits for the Next Century) exhibition held at the Galerie Le Barc de Boutteville in late 1893, Jules Christophe extolled 'this exquisite zone of freedom, this wonderful whiff of anarchy! What seemingly fraternal individualism. The followers of Ingres rub shoulders with the friends of Georges Seurat'.

The Belgian artists Théo Van Rysselberghe and Georges Lemmen are considered to be the movement's principal portraitists. Van Rysselberghe's first Neo-Impressionist portrait, painted in 1888, a full-length study of Alice Sèthe, the daughter of a leading Brussels industrialist, was hailed by a critic as 'the most satisfying work on display' when it was shown at the Les XX exhibition in Brussels in 1889. Other portraits met with less success - the provincial painter Achille Laugé, who worked in the south of France near Carcassonne, saw his Neo-Impressionist portraits regularly rejected by exhibition juries in Paris. Van Rysselberghe was also to complain about clients who sought to entice him back towards more traditional methods of portraiture, lamenting: 'Nothing annoys me more than when fools tell me: I just adore what you do, but want you to do something else'.

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