Quantitative and qualitative modifications of tannins and anthocyanins in grape skin were investigated at different dates of harvest, from berries sorted on the basis of their density. Free anthocyanins accumulated until 170 g/L of sugars in pulp before undergoing a slight decrease. Changes in anthocyanin composition were observed with increasing sugar levels in the pulp that reflected structural differences between classes of anthocyanins. The proportion of methoxylated anthocyanins continued to increase in the skin as sugar accumulated while the proportion of coumaroylated anthocyanins initially increased (up to 200 g/L of sugars in the pulp) and then rapidly decreased. In comparison, no major quantitative nor qualitative change was observed for tannins, except for a slight increase of the mean degree of polymerization. Whatever the physiological stage of the pulp, the extraction yield of skin phenolics into hydroalcoholic solution for 5 h was lower than 77% for anthocyanins and 38% for proanthocyanidins. For both classes of compounds, no clear evolution in these extraction yields could be observed as sugars accumulated in pulp (from 162.6 to 275.0 g/L). Nevertheless, some structural features within each family of compounds significantly influenced extractability, for example, a lower extraction yield for coumaroylated anthocyanins and for tannins with a high degree of polymerization. Finally, no direct relationship could be found in extraction media between the amounts of all red pigments (measured in acidic conditions) and the color intensity at 520 nm (measured in wine-like model solutions).