Hexavalent chromium from industrial residues is highly mobile in soil and can lead to the contamination of groundwater through runoff and leaching after rainfall. This paper focuses on the three-dimensional (3D) electrokinetic remediation (EKR) of chromium-contaminated soil from an industrial site. Activated carbon particles coupled with Fe ions (AC-Fe) were used as the third electrode. The optimum dose ratio of the electrode particles and remediation time were selected on the basis of single-factor experiments. X-ray photoelectron spectroscopy (XPS) analysis was carried out to explore the reduction of Cr(VI) on the surface of the electrode particles (AC-Fe). The results showed that AC-Fe had a positive effect on Cr(VI) reduction with a removal rate of 80.2%, which was achieved after 10 d by using a 5% dose of electrode particles. Finally, it was concluded that the removal mechanism combined the processes of electromigration, electrosorption/adsorption and reduction of Cr(VI) in the 3D EKR system.