Hexavalent chromium existing in wastewater has severe toxic effects on the human body. Reductive detoxification and adsorption of hexavalent chromium have increasingly become important research areas. In this study, Zr-based metal–organic frameworks are investigated as new photocatalysts for the photocatalytic reduction of Cr(VI); the catalysts are expected to integrate the high efficient reductive ability of nano-scale Zr–O clusters with the visible light photoexcitation ability of the OH-containing organic molecules. The designed Zr-based MOFs were successfully synthesized via a facile solvothermal route and then were comprehensively investigated via XRD, FT-IR, SEM, EDS, BET, and TG characterization techniques. The photocatalytic reduction tests demonstrated that the as-synthesized Zr-based MOF materials can rapidly reduce and totally remove Cr(VI) from water containing 8 ppm Cr(VI) under visible light using only 10 minutes of irradiation time. Through a comparative photocatalytic reduction examination, it was found that the two OH groups in the organic molecules played a key role in the visible-light photocatalytic reduction process. This study explored a new way to employ high catalytic ability of nano-scale materials by avoiding their agglomeration and photoexcitation ability of organic molecules simultaneously, which will contribute to the research on photocatalytic materials.