ZnO–graphene composites are successfully synthesized via microwave-assisted reaction of zinc sulfate in aqueous solution with a graphite oxide dispersion using a microwave synthesis system. Their morphology, structure and photocatalytic performance in reduction of Cr(VI) are characterized by scanning electron microscopy, X-ray diffractionspectroscopy and UV-vis absorption spectrophotometer, respectively. The results show that in the composite the graphenenanosheets are decorated densely by ZnOnanosheets, which display a good combination between graphene and ZnOnanosheets. The ZnO–graphene composite exhibits an enhanced photocatalytic performance in the reduction of Cr(VI) with a removal rate of 98% under UV light irradiation as compared with pure ZnO (58%) due to the increased light absorption intensity and range, as well as the reduction of electron–hole pair recombination with the introduction of graphene.