Anodic oxidation and paired electrochemical oxidation of anthracene to anthraquinone in an undivided cell were carried out. The factors affected on the paired electrochemical oxidation of anthracene to anthraquinone were explored. The results revealed that oxygen flow rate, concentration of sulfuric acid and agitation rate were the major factors, and concentration of mediator, temperature, and current density were the minor factors. The reaction mechanism of paired electro-oxidation of anthracene was proposed. Oxygen was cathodically reduced to generate H2O2which chemically reacted with V4+to produce both OH free radical and V5+. Which then oxidized anthracene to anthraquinone. The results also showed that the total current efficiency of anthraquinone was higher than 100%.