We examined the use of a bismuth–glassy carbon (Bi/C) composite electrode for the determination of trace amounts of lead and cadmium. Incorporated bismuth powder in the composite electrode was electrochemically dissolved in 0.1M acetate buffer (pH 4.5) where nanosized bismuth particles were deposited on the glassy carbon at the reduction potential. The anodic stripping voltammetry on the Bi/C composite electrode exhibited well-defined, sharp and undistorted peaks with a favorable resolution for lead and cadmium. Comparing a non-oxidized Bi/C composite electrode with an in-situ plated bismuth film electrode, the Bi/C composite electrode exhibited superior performance due to its much larger surface area. The limit of detection was 0.41μg/L for lead and 0.49μg/L for cadmium. Based on this study, we are able to conclude that various types of composite electrodes for electroanalytical applications can be developed with a prudent combination of electrode materials.