Layered double hydroxides (LDH) are the cost-effective and high-efficiency materials for remediation of potentially toxic elements (PTEs) in contaminated soil and groundwater. Herein, the effectiveness and mecha-nisms of a ternary Ca-Mg-Al LDH (CMAL) for the synergistic remediation of As, Cd, and Pb were investigated in contaminated soils and simulative groundwaters for the first time. The immobilization efficiencies of As, Cd, and Pb in both black soil (BS) and red soil (RS) amended by CMAL at 5 wt% were all > 75%. CMAL amendment transferred more mobile As, Cd, and Pb fractions in soils to immobile species than did Ca-Al LDH and Mg-Al LDH treatments. Furthermore, using a pump-and-treat technology, 82-98% of these 3 PTEs from contaminated groundwater were successfully immobilized in both CMAL treated BS and RS top-soils. Meanwhile, leaching of Ca, Mg, and Al from CMAL was minimal indicating the material was stable. The excellent immobilization per-formance of CMAL for these PTEs was attributed to the coating of soil microparticles by CMAL nanosheets that allowed complexation of Ca-O-As/Cd or Mg-O-As/Cd/Pb formation, co-precipitation of Ca/Fe-As and Cd(OH)2 , and formation of Ca-bridged ternary complex (FeO-Ca-As/Cd). The adverse effect of oppositive pH/Eh-dependence between As and Cd/Pb was overshadowed by these mechanisms and thus allowed As immobiliza-tion. Immobilization of As, Cd, and Pb by CMAL amendment was more favorable for RS soil due to its lower reduction potential and more participation of metal-(hydr)oxides for complexation. Overall, the ternary-LDH is a promising synergistic remediation strategy for multi-PTEs contaminated soil and groundwater.