An electrochemical study of lyophilized blueberry (Vaccinium corymbosum L.) and raspberry (Rubus idaeus L.) fruits was carried out using microparticulate deposits from ethanolic extracts of fruits in contact with different aqueous electrolytes. This voltammetry is dominated by the oxidation of anthocyanins. It was hypothesized that under conditions of electrochemical generation of reactive oxygen species (ROS), new anthocyanin-derived species with high antioxidant capacity are formed over a wide pH range. In the case of ROS-activated anthocyanins, electrochemical oxidation is associated with loss of sugar moieties. Experimental voltammetric and scanning electrochemical microscopy (SECM) imaging data consistent with this hypothesis are presented.