Capillary electrophoresis (CE) has been widely applied to the separation and determination of different metal species, and has proved to be a fast, high-resolution separation technique [26–31]. The detection methods typically used in combination with CE separation technique are ultraviolet light (UV), fluorescence or laser-induced fluorescence (LIF) detection. The lack of a strong chromophore from metal ions has certainly been one of the major limitations in the analysis of most metals by these methods. In addition, these detection modes suffer from lack of sensitivity when a miniaturized device is used. Electrochemical detection (ED) offers high sensitivity and selectivity for metals that are readily oxidized or reduced. This technique is readily suitable and compatible with microfabrication technology that has been successfully employed in microchip CE.