This work aimed to characterize and discriminate genealogical groups of coffee as to the chemical composition of the grains through the model created by PLS-DA method. 22 accessions of Coffea arabica, from the Active Germplasm Bank of Minas Gerais, were divided into groups according to the genealogical origin. Samples of ripe fruits were harvested selectively and processed by the wet method, to obtain pulped coffee beans, with 11% (b.u.) of water content. The raw beans were assessed as to the content of polyphenols, total sugars, total lipids, protein, caffeine, sucrose, and fatty acids. The data were submitted the chemometric analysis, PCA and PLS-DA. The results of PLS-DA identified the variables which most influence the classification of genealogical groups and possible chemical markers to accessions processed by the pulped method. The sucrose content was an important marker for the Exotic accession group. However, the content of polyphenols has been identified as a marker for the group Tymor Hybrid, and the caffeine for the bourbon group. The different fatty acids have been identified as markers for all genealogical groups, at different levels. The model PLS-DA is effective in discriminating genealogical groups from the chemical composition of the beans.