TiO₂-reduced graphene oxide (RGO) composites are successfully synthesized via the microwave-assisted reduction of graphite oxide in a TiO₂ suspension using a microwave synthesis system. Their morphology, structure and photocatalytic performance in the reduction of Cr(VI) are characterized by scanning electron microscopy, transmission electron microscopy, atomic force microscopy, X-ray diffraction spectroscopy and UV-vis absorption spectrophotometer. The results show that in the composite the RGO nanosheets are densely decorated by TiO₂ nanoparticles, which displays a good combination between RGO and TiO₂. TiO₂–RGO composites exhibit enhanced photocatalytic performance for the reduction of Cr(VI) with a maximum removal rate of 91% under UV light irradiation as compared with pure TiO₂ (83%) and commercial TiO₂ P25 (70%) due to the increased light absorption intensity and range as well as the reduction of electron-hole pair recombination in TiO₂ with the introduction of RGO.