Abstract: In this article, results using confocal µ-Raman to analyse the cross-section of paint samples are presented. Results obtained with light microscopy, scanning electron microscopy (SEM) combined with an energy dispersive X-ray analysis (EDX) and micro-X-ray fluorescence (µ-XRF) are mentioned and compared to the ones obtained with confocal (MRS). In some cases, pigment identification was possible only by combining analytical results from different techniques. The samples were drawn from five paintings belonging to the Academy of Fine Arts of Antwerp, which are part of a collection of 34 paintings made by students from the Academy between 1819 and 1920. Since, on the one hand, the painting techniques and materials, especially pigments, used in this period are still not completely known, and on the other hand, this collection constitutes a very important and reliable resource of information, these paintings were chosen for a systematic investigation. They represent the evolution of painting in Belgium over approximately a century.