The electroless copper plating solution containing ethylenediaminetetraacetic acid disodium salt (EDTA×2Na) and potassium sodium tartrate (TART) as complexing agents was measured by electrochemical workstation, and the effects of complexing agents and 2,2￠-bipyridine on cathode and anode polarization were examined. The results show that the anodic reaction is controlled by both chemical reaction and diffusion, while the cathodic reaction is mainly controlled by diffusion. Through the complexation competition and discharge competition between them, EDTA×2Na and TART affect the polarization. The diffuse electrical double layer on the surface of the electrode is affected by 2,2￠-bipyridine through adsorption and AC impedance, which ultimately impacts the copper deposition reaction. Under the optimum solution composition of 13.35 g/L of EDTA×2Na, 13.35 g/L of TART and 15 mg/L of 2,2′-dipyridyl, the average deposition rate can reach 14.83 mg/min. The copper film deposited on substrate has excellent properties.