The phenolic composition of skins and seeds from Vitis vinifera L. cv. Carménère and Cabernet Sauvignon grapes during ripening was evaluated by high-performance liquid chromatography-diode array detection and spectrophotometric analysis. As compared to Cabernet Sauvignon grape skins, Carménère grape skins presented higher contents of total anthocyanins, monomeric flavan-3-ols, and total flavonoids, a higher mean degree of polymerization, a higher percentage of galloylation, a higher average molecular weight of the flavanol fraction, and a higher color intensity. As compared to Cabernet Sauvignon grape seeds, Carménère grape seeds presented a lower content of monomeric flavan-3-ols, a higher mean degree of polymerization, a higher percentage of galloylation, a higher average molecular weight of the flavanol fraction, a lower content of (+)-catechin, and higher contents of (-)-epicatechin, epicatechin-3-O-gallate, gallic acid, and dimeric procyanidins esterified with gallic acid. Altogether, we conclude that Carménère grapes present a differential composition and evolution of phenolic compounds when compared to Cabernet Sauvignon grapes.