The low-toxicity treatment of chromium-containing wastewater represents an important way of addressing key environmental problems. In this study, a core-shell structural ZIF-8@TiO2 photocatalyst was synthesized by a simple one-step hydrothermal method. The obtained composite photocatalyst possessed improved photocatalytic activity compared with TiO2. The results indicated that the optimized ZIF-8@TiO2 composite exhibited the highest removal efficiency with 93.1% of Cr(VI) after 120 min under UV-vis irradiation. The removal curves and XPS results indicated that the adsorbed Cr(VI) on the ZIF-8 during the dark process was preferentially reduced. The superior removal efficiency of ZIF-8@TiO2 is attributed to the combination of both high adsorption of ZIF-8, which attracted Cr(VI) on the composite surface, and the high separation efficiency of photo-induced electron-hole pairs. For the mixture of wastewater that contained methyl orange and Cr(VI), 97.1% of MO and 99.7% of Cr(VI) were removed after 5 min and 60 min light irradiation, respectively. The high removal efficiency of multiple pollutants provides promising applications in the field of Cr(VI) contaminated industrial wastewater treatment.