ABSTRACT: Intermolecular copigmentation is one of the mechanisms of stabilization of anthocyanins in nature and is also responsible for the characteristic color and stability of aged red wines. In the present study, the effect of polyphenol oxidase (PPO) activity on phytochemical stability of an ascorbic acid-fortified muscadine grape juice following high hydrostatic pressure (HHP) processing (400 and 550 MPa for 15 min) and after 21 d of storage at 25 °C was investigated. Addition of rosemary and thyme polyphenolic extracts (copigmentation) was evaluated as a means to stabilize anthocyanins and ascorbic acid during pressurization and subsequent storage. Polyphenolic extracts were partially purified in order to reduce their content of PPO substrates, and improve their stabilization properties within juice matrix. Overall PPO activity increased (3- and 2.5-fold) following HHP at 400 and 550 MPa, respectively, although it was significantly lower in copigmented treatments. Higher anthocyanin losses occurred at 400 (∼70%) than at 550 MPa (∼46%), which were correlated to antioxidant losses (r= 0.89). Similarly, greater ascorbic acid losses were observed at 400 (84%) than at 550 MPa (18%). Copigmentation increased anthocyanin retention in reference to pressurized controls (3- and 3.2-fold for rosemary and thyme treatments, respectively) and decreased ascorbic degradation (20 to 32%). In stored samples, higher anthocyanin content (>2-fold) and antioxidant capacity (>1.5-fold) was observed for copigmented treatments when compared to control juices. Addition of partially purified copigments increased muscadine grape juice color, antioxidant activity and also reduced phytochemical losses during HHP processing and storage.