Variations in water chemistry may lead to the release of harmful heavy metals in drinking water distribution systems (DWDSs). In this study, the effects of chloride on the release of heavy metals such as Fe, Mn, As, Cr, Mo, V, Sr, and Co were examined using steel and cast iron pipe loops. After chloride was added, the relative contents of goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and siderite (FeCO3) in pipe scales increased, but the contents of magnetite (Fe3O4) decreased. The most prevalent compounds were α-FeOOH and γ-FeOOH. When the chloride levels were increased, the effluent concentrations of Fe, Mn, As, Cr, Mo, V, Sr, and Co significantly increased. These heavy metals were released presumably because of the destabilization and dissolution of corrosion scales induced by chloride and adsorption site competition. Strong positive correlations were also observed between Fe&Mn, Fe/Mn&As, Fe/Mn&Cr, Fe/Mn&Mo, Fe/Mn&V, Fe/Mn&Sr, and Fe/Mn&Co, indicating the co-release of Fe, Mn, and other metals. This study may be helpful for the potential strategies on avoidance of heavy metal release and improvement of water supply security.