A formal compositional study of the proanthocyanidins of Vitis vinifera L. cv. Carménère was conducted in this work. We first characterized the polymeric proanthocyanidins of Carménère skins, seeds, and wines. In addition, the wine astringency was analyzed and compared with Cabernet Sauvignon. Although Carménère wines had a higher proanthocyanidin concentration and mean degree of polymerization than Cabernet Sauvignon wines, the former wines were perceived as less astringent. The low seed/skin proportion in Carménère wines as compared to other varieties, as evidenced by the reduced number of seeds per berry and the higher amount of epigallocatechin subunits of Carménère wine proanthocyanidins, could explain this apparent paradox.