This research included experiments on the advanced treatment of coking wastewater by electrochemical reactor. The results showed that a favorable operating condition could be obtained through the electrochemical course, when electrolysis time was 60 min, current density was 8 A, and electrode span was 1 cm. Under this condition, total organic carbon (TOC) removal efficiency could reach 73%, and the removal mechanism had also been analyzed. In addition, the electrodes’ morphology characteristics and components were analyzed through a scanning electron microscope, and the results showed that on the surface of anode and cathode electrodes there were quite a few cracks, the amount of which increased after use. Meanwhile, the content of chemical elements on the electrodes’ surface changed obviously after use – especially Ti content (from 39.66% to 92.69%) on the anode and Fe content (from 72.57% to 53.66%) on the cathode. The result was probably caused by the redox reaction, namely the shedding of the coating on the anode electrode’s surface, and reactions around the cathode electrode’s surface.