During red wine maturation in contact with oak wood, C-glucosidic ellagitannins can react with anthocyanins, leading to new pigments. In this work the thermodynamic and kinetic constants of the network pH-dependent equilibrium of a new myrtillin (delphinidin 3-O-glucoside)–vescalagin hybrid pigment (1-deoxyvescalagin-(1β→8)-myrtillin) have been determined by UV–visible absorption and stopped-flow experiments and compared to those determined for myrtillin. The vescalagin substitution at the C-8′ center of myrtillin entails important variations in the pigment behavior upon pH changes. The hybrid pigment showed lower pK′a and pK a values and a much higher value of K t. As a consequence, at moderately acidic pH values (4 < pH < 6), the percentage of the hemiketal is much lower and the quinoidal base and the (E)-chalcone represent higher percentages relative to those for myrtillin. Therefore, the hybrid pigment can provide in slightly acidic or neutral solutions an exceptionally different color compared to that of myrtillin.