Phenoxyl radical was generally suggested as the intermediate during copper-catalyzed aerobic oxygenation of phenols. However, the substrate-dependent selectivity has not been well interpreted, due to insufficient characterization of the radical intermediate under reaction conditions. When studying the CuCl-LiCl-catalyzed aerobic phenol oxidation, we obtained EPR spectra of phenoxyl radicals generated by oxidizing phenols with the preactivated catalyst. Upon correlation to the selectivity of benzoquinone, the hyperfine coupling constant of para-site proton (aH, para) was found to be better than the Hammett constant. The catalysis mechanism was studied based on EPR detection and the reaction results of phenoxyl radicals under N2 or O2 atmosphere. It appeared that the chemoselectivity depended on the attack of activated dioxygen on phenoxyl radicals, and the activation of dioxygen by [CunCln+1]- (n = 1, 2, 3) was suggested as the rate-determining step. Understanding of the substrate-dependent selectivity contributed to predicting the chemoselectivity in the aerobic oxidation of phenols.