The photocatalytic reduction efficiency of hexavalent chromium (Cr2O72- (Cr(VI)) is suffering from high recombination of photoinduced charges, poor adsorption capacity of Cr(VI), and slow desorption of product trivalent chromium (Cr3+ (Cr(III))) from photocatalyst surface. In this work, carbon dots (CDs) was coupled with TiO2 mesocrystals (MT), where CDs displayed both the electron collectors and the active sites. During photo reduction of Cr(VI), the as-prepared CD/MT exhibited activity about 5.4 times higher than the pure TiO2 mesocrystals. The positive charges on the CD/MT surface favored the selective adsorption of Cr(VI) and rapid desorption of Cr(III), which has an obvious promotion on the photocatalytic reduction of Cr(VI) and retention of photoreduction activity. Meanwhile, the CDs coupled on TiO2 mesocrystals facilitated the separation of photogenerated charges. This work provides a simple and effective adsorption-photoreduction-desorption mechanism for the photocatalytic reduction of Cr(VI).