A Pd/C gas-diffusion cathode which generated H2O2 through a two-electron reduction process of fed oxygen molecule was used to degrade 4-chlorophenol in an undivided electrolysis device. The kinetics of 4-chlorophenol degradation has been investigated by the electrochemical oxidation processes. By inspecting the relationship between the rate constants (k) and influencing factors, using first-order kinetics to describe the electrochemical oxidation process of 4-chlorophenol, a kinetic model of 4-chlorophenol degradation process was proposed to calculate the 4-chlorophenol effluent concentration: C = C0 exp( -3:76 × 10(-6) C(-0.5)0 J(2) M(-0.7) Q(0.17) Dt). It was found that the electrocatalytic degradation rate of 4-chlorophenol was affected by current density, electrode distance, air-feeding rate, electrolyte concentration and initial 4-chlorophenol concentration. The kinetics obtained from the experiments under corresponding electrochemical conditions could provide an accurate estimation of 4-chlorophenol effluent concentration and lead to better design of the electrochemical reactor.