To improve accuracy in the determination of anthocyanin purity and succeeding antioxidant capacity, 1H and 13C nuclear magnetic resonance spectroscopy have been combined with high-performance liquid chromatography (HPLC) equipped with a diode array detector and UV-vis spectroscopy in the analysis of anthocyanidin 3-glycosides and 5-carboxypyranoanthocyanidin 3-glycosides. The molar absoptivity (epsilon) values were found to be relatively similar, in contrast to previously reported literature values, and the average epsilon values for both anthocyanidin 3-monoglycosides and 5-carboxypyranoanthocyanidin 3-glycosides were proposed to be 22,000 and 23,000 in acidified aqueous and methanolic solutions, respectively. To assess the influence of structure on the potential antioxidant capacity of anthocyanins, the 3-glucosides of pelargonidin (1), cyanidin (2), peonidin (3), delphinidin (4), petunidin (5), malvidin (6), 5-carboxypyranopelargonidin (8), 5-carboxypyranocyanidin (9), 5-carboxypyranodelphinidin (11), 5-carboxypyranopetunidin (12), and 5-carboxypyranomalvidin (13) and the 3-galactosides of cyanidin (7) and 5-carboxypyranocyanidin (14) were examined by a ferric ion reducing antioxidant power (FRAP) assay. The reducing capacities of the individual anthocyanins were in the range of 0.9-5.2 micromol of Trolox equivalents/micromol. The two 5-carboxypyranoanthocyanins 11 and 9 and the four common anthocyanins 2, 4, 7, and 14, all possessing pyrogallol or catechol type of B rings, showed the highest antioxidant capacity measured by FRAP. However, the inclusion of the 5-hydroxyl in the D ring and just one oxygen substituent on the B ring in 8 diminished the reducing capacity considerably. Correspondingly, electrochemical behavior of 5-carboxypyranoanthocyanidin 3-glucosides and anthocyanidin 3-glucosides was derived using HPLC coupled to a coulometric array detector set from 100 to 800 mV in increments of 100 mV. The relative order of the reducing capacity of the various 5-carboxypyranoanthocyanidin 3-glucosides and anthocyanidin 3-glucosides were nearly alike, whether determined by coulometric array detection or FRAP.