Mercury films were precoated on the surface of glassy carbon electrodes and the contents of Cu, Zn, Cd and Pb in mixed solutions were determined based on the anodic-stripping voltammetric method. The response regularities of mercury film electrodes prepared under various film coating solution concentrations, PH and film coating times to the stripping current of Cu, Pb, Cd and Zn were discussed. The results reveal that, when the concentration of film coating solutions is 0.03 mol/L and the film coating times is 3, the stripping peaks of all the four heavy metallic ions have moderate peak heights without noise waves. When the pH value of the base solution is 4.68, the position of stripping peaks is suitable and beneficial to the improvement of determination accuracy. Mercury film coated electrodes with stable performances to conduct simultaneous determination of Cu, Pb, Cd and Zn heavy metallic ions were prepared under the selected optimum condition. The results prove that these electrodes have good repeatability. The concentration of Zn2+ presents a good linear relationship with the peak current. When the preconcentration time is increased to 10 min, these electrodes are able to determine Cd2+ with their concentrations as low as 0.001 mg/L.