The process optimization and characteristics of electrode-biofilm for the treatment of copper pickling wastewater in the self-designed reactor were experimentally investigated. Carbon electrodes were installed in the reactor as the anode and cathode and denitrifying microorganisms were fixed on the surface of the cathode. The results showed that neutralization, copper ion removal, denitrification proceeded simultaneously and no secondary pollution existed. The removal rate of total nitrogen and copper ion in the effluent water reached 98% and 97% at 30mg/L of copper ion concentration and 100mg/L of nitrate nitrogen when the conditions were controlled at temperature 35°C, current density 0.1mA/cm2, hydraulic retention time 11h and C/N ration 1.07. The pH value of the treated water was increased almost to neutral. In addition, copper ion solution of certain concentration and purity could be made by exchanging the polarity of anode and cathode to recycle copper in this research.