Condensed tannins play a major role in the quality of red wine. After grape extraction, they quickly evolve thanks to different oxidation mechanisms. Recently, NMR identified a new sub class of condensed tannins, named crown procyanidins, in red wine. The crown procyanidins’ tetramer exhibits a macrocyclic structure composed of four (-)-epicatechin with an unusual cavity in the center of the molecule. These new tannins exposed a higher polarity than the linear tannins. In this work, the evolution kinetics of these crown procyanidins during the winemaking process and after aging of red wine in bottles were studied. Samples’ quantification was analyzed by UPLC-UV-Q-TOF. The concentration of cyclic and non-cyclic procyanidins was compared. During the winemaking process, crown procyanidins are mainly extracted at the beginning of the alcoholic fermentation and they remain stable until the end of the winemaking process. The high polarity and solubility of this new molecule in water was confirmed. During the aging of red wine in bottles, crown procyanidins’ concentrations are stable, whereas the non-cyclic tannins decrease dramatically. Finally, a strong oxygenation experiment confirmed the crown procyanidins’ resistance to oxidation and unique skills.