A novel system combining photocatalysis and capacitive deionization (CDI) was proposed and used to efficiently remove the total Cr from the aqueous solution for the first time. MIL-53(Fe) with wide visible-light absorption was successfully prepared by a simple solvothermal method, and applied as positive photoelectrode material of the photocatalysis-CDI system (PCS) to convert Cr(VI) to Cr(III). Active carbon was used as negative electrode material to absorb Cr(III). An enhanced removal of Cr(VI) can be obtained by applying visible light irradiation and 1.3 V direct current (DC) voltage simultaneously and the Cr(VI) removal can reach a maximum value of 81.6%, much higher than those under individual 1.3 V DC voltage (39.4%) or visible light irradiation (54.2%), demonstrating the synergistic effect from CDI and photocatalysis. More importantly, effective removal of the total Cr with high removal ratio (72.2%) can be achieved, which is difficult to be realized using current other technologies. The strategy in this work provides a promising method for the complete removal of high-valence heavy metal ions.