In this study, the permeable-reactive-barrier (PRB) assisted electrokinetic (EK) was used to remediate As/Cr Cocontaminated soil, aiming to explore the optimal remediation conditions and the migration of As/Cr. The effects of PRB active substance, PRB location, voltage gradient and running time on the migration and transformation of Cr and As in simulated As/Cr contaminated kaolin were studied. The optimal parameters were as follows: PRB position was located near the anode (PRB A, the medium of PRB was hydrocalumite (CaAl-LDH)), initial voltage gradient was 1 V/cm, running time was 96 h. Under the optimal conditions, the removal efficiency of total arsenic (TAs) and total chromium (TCr) were 40.1% and 81.0%, respectively. This indicated that EK can effectively migrate As and Cr, and PRB can effectively adsorb As and Cr. The migration of As tends to both anode and cathode, while Cr tends to migrate towards the anode. The XRD patterns and FTIR spectra confirmed that the As immobilized by CaAl-LDH was mainly adsorbed on the surface, while Cr existed in CaAl-LDH by surface adsorption and intercalation.