Using a self-made Pd/C gas-diffusion electrode as the cathode and a Ti/IrO2/RuO2 anode, the degradation of 4-chlorophenol has been investigated in an undivided electrolysis device by the electrochemical oxidation processes. The result indicated that the neutral aqueous solutions can accelerate 4-chlorophenol degradation during electrolysis. The removal efficiency of 4-chlorophenol and COD reached about 89.6% and 62.0% after 120 min electrolysis, respectively. It suggested that most of 4-chlorophenol was oxidised to intermediates using the Pd/C gas-diffusion electrode. Furthermore, the biodegradation ability of the solution was increased significantly during the electrolysis. The degradation of 4-chlorophenol was attributed to the cooperative oxidation processes including electrochemical oxidation at the anode and H2O2 and hydroxyl radical (HO·) produced by the reduction of oxygen at the cathode. Finally, main aromatic intermediates (e.g., hydroquinone and benzoquinone) and main aliphatic carboxylic intermediates (e.g., oxalic, malonic, maleic, succinic, fumaric, and dodecanoic acids) were identified by GC-MS. Moreover, a reaction scheme involving all these intermediates was proposed.