The electrochemical oxidation of pulp and paper making wastewater assisted by transition metal (Co, Cu) modified kaolin in a 200 ml electrolytic batch reactor with graphite plate as electrodes was investigated. H(2)O(2), which produced on the surface of porous graphite cathode, would react with the catalysts to form strong oxidant (hydroxyl radicals) that can in turn destroy the pollutants adsorbed on the surface of kaolin. The transition metal (Co, Cu) modified kaolin was also characterized by XRD and SEM before and after the modification and the results showed that the transition metals were completely supported on kaolin and formed a porous structure with big BET surface. The mechanism was proposed on the basis of XPS analysis of the catalyst after the degradation process. Series of experiments were also done to prove the synergetic effect of the combined oxidation system and to find out the optimal operating parameters such as initial pH, current density and amount of catalyst. From the results it can be founded that when the initial pH was at 3, current density was 30 mA cm(-2); catalyst dose was 30 g dm(-3), COD (chemical oxygen demand) removal could reach up to 96.8% in 73 min.