The co-contamination of arsenic (As) and cadmium (Cd) in the environment is of most concern. In this work, poorly crystalline CaFe-layered double hydroxide (CaFe-LDH) was synthesized with a Ca-to-Fe molar ratio of 4 to ensure effective immobilization of Cd and As in soil. The application of Ca 4 Fe-LDH in soil remediation demonstrated that the targeted heavy metals gradually mineralized into a relatively stable oxidizable and residual state. At a soil remediation dosage of 1.6%, the availability levels of Cd and As decreased significantly, achieving stabilization efficiencies of 99% and 85.2% respectively. Cd is trapped through isomorphic substitution and dissolution-reprecipitation of calcium (Ca) laminate, resulting in the formation of CdCaFe-LDH mineralization products. As is immobilized through ion exchange with interlayer anions, redox with Fe(III), and Fe-Cd-As complexation. Moreover, the results of the characterization and density functional theoretical (DFT) calculations demonstrate that the CdCaFe-LDH formed by isomeric substitution of Ca for Cd enhanced the adsorption of As on the (110) plane of LDH, indicating that the trap mechanism of Cd and As by Ca 4 Fe-LDH is synergistically promoted. Overall, the above results prove that mineralization using Ca 4 Fe-LDH is a promising method to remediate soils combined contaminated by both Cd and As.