Qualitative and quantitative analysis of trace heavy metals in aqueous environment are rapidly assuming significance along with the rapid development of industry. In this paper, gold microelectrode array (MEA) plated with mercury film was used for simultaneous voltammetric detection of zinc, cadmium, lead and copper ions in water. The electrochemical behavior and the actual surface area of the MEA were investigated by cyclic voltammetry in K3[Fe(CN)6]. Electrochemical impedance spectrum (EIS) was utilized to examine the deposition of mercury on the electrode surface. Based on anodic stripping voltammetry, mercury film-Au MEA was applied to the detection of heavy metals in artificial analyte, where good calibrate linearity was obtained for cadmium, lead and copper ions, but with zinc exhibiting poor linearity.