In this work, four artworks dating from the 19th century by Brazilian painters Firmino Monteiro, Henrique Bernardelli, and Eliseu Visconti were analyzed by MA-XRF. Pb-L, Fe-K, and Hg-L were the main elemental maps obtained in all paintings. In the artworks of Henrique Bernardelli and Eliseu Visconti, maps of Cr-K and Co-K were also obtained. These results indicate that these Brazilian painters from the 19th century used few pigments to create their paintings, with the different hues coming mainly from ocher pigments. Using correlation image methods, no intentional mixtures of pigments made by the painters were found. These results indicate that the three painters used similar materials and techniques for preparing their pigments. These similarities are confirmed through statistical analysis by non-negative matrix factorization (NMF). In this method, it was possible to verify that the main bases of the contribution of the data registered in each artwork are the same. The analysis also revealed that one of Eliseu Visconti’s paintings had an underlying painting, and another artwork by Eliseu Visconti contained a golden pigment with Cu and Zn. These results have helped art historians and conservators understand the creation process of Brazilian artists in the 19th century.