The gaining of new knowledge about varietal differences in grapevines can be useful for the designing of genetic improvement programs. More and more, chemical methods complement ampelographic ones in the study of variability in grapevines. This work is aimed at the anthocyanin profiling of red-coloured grapes, of which ca. 120 cultivars were sampled; among these there were a high number of old Italian vines and 30 Vitis vinifera ssp. silvestris originating from different areas of Italy. Anthocyanins were HPLC separated and quantified with the aid of an inverse phase microbore column and a photodiode detector. Grapevines were numerically separated in groups using as indexes the percentage of the 5 monoglucosides present, the summations of: acetic esters; malvidin-3-monoglucoside-caffeoate plus all 5 p-coumaric esters; as well as a series of relations correlated to certain enzymatic activities necessary for the esterification of glucosides, hydroxylation and methylation in the biosynthesis of several anthocyanins. Data derived from the study of indexes of varietal enzymatic activity enable us to qualify differences between grapevines linked to the synthesis of anthocyanins. The stability of anthocyanic profiles within the same grape variety enables the use of this technique for taxonomic purposes. This research study discusses the use of this technique for classification and analysis of grape phylogenesis. An in-depth look into the relations between cultivated and wild varieties is given