Deactivations of two different kinds of anodes during electrochemical oxidation of p-chlorophenol (p-CP) were investigated by using electrochemical measurement, and their corresponding oxidation mechanisms were also discussed. The results indicated that p-CP could be oxidized directly on both the Pt (“I”type anode) and PTFE (polytetrafluoroethylene)-β-PbO2 (“II”type anode), however, the electro-catalytic activities of both anodes lost immediately. Electrolysis at high potential could recover the electro-catalytic activities of both anodes, and Pt needed higher potential than PTFE-β-PbO2 did. The deactivated Pt could also recover its activity by soaking it in ordinary organic solvents such as acetone, tetrahydrofuran, dimethyl sulfoxide, but deactivated PTFE-β-PbO2 could not. For Pt anode (“I”), besides the direct oxidation of p-CP, oxygen transfer reaction was the main cause for the removal of p-CP when anodic potential was higher than 2.0 V; for PTFE-β-PbO2 anode (“II”), besides the direct oxidation reaction, the oxidative reaction of hydroxyl radical became the main cause for the removal of p-CP when anodic potential was higher than 1.8 V.