Multifunctional gas-diffusion electrode with electrochemical reduction and oxidation properties was achieved based on the palladium-modified activated carbon (Pd/C). Pd/C catalysts were prepared using the formaldehyde reduction from nitric acid treated activated carbon and fully characterized by Boehm titration method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and cyclic voltammetry (CV) techniques. The electrochemical degradation of three typical chlorinated phenols (4-chlorophenol, 2,4-dichlorophenol and pentachlorophenol) was investigated in a diaphragm electrolysis system with the Pd/C gas-diffusion electrode as a cathode, feeding firstly with hydrogen gas and then with air. The electrolysis system with 15% mass fraction nitric acid pretreated activated carbon showed better electrocatalytic activity compared to those from other mass fractions nitric acid, due to the active organic function groups increased on the surface of the activated carbon. When the ratio of Pd/C was low, Pd particles with an average size of 3.5 nm were highly dispersed in the activated carbon with an amorphous structure. The Pd/C gas-diffusion cathode cannot only reductively dechlorinate chlorinated phenols by feeding hydrogen gas, but also accelerate the two-electron reduction of O-2 to H2O2 by feeding air. Therefore, the removal efficiency of chlorinated phenols reached almost 100%, conforming to the sequence of 4-chlorophenol, 2,4-dichlorophenol and pentachlorophenol. The dechlorination of three chlorinated phenols exceeded 80% after 100 min. For H2O2 and HO center dot existed in the catholyte, the mineralization of organic pollutants in the cathodic compartment was better than that in the anodic compartment. Finally, chlorinated organic pollutants were efficiently degraded by the combined processes of reduction and oxidation in the present system. (C) 2012 Elsevier B.V. All rights reserved.