MIL-53(Fe)–reduced graphene oxide (rGO) hybrid materials with different rGO contents were prepared through a simple one-step solvothermal method. The products were characterized by X-ray diffraction patterns, thermal analysis, FT-IR spectra, Raman spectroscopy, scanning electron microscopy, UV-vis absorption spectra and photoluminescence spectra. The hybrid with 2.5% rGO content showed optimal photocatalytic performance in degradation of methylene blue under both UV and visible light irradiation and the degradation rate constants under UV and visible light were 1.34 and 1.57 times of those using MIL-53(Fe) respectively. The considerable promotion in photoactivities can be attributed to rGO being able to separate the photogenerated electrons and suppress electron–hole recombination. In addition, the hybrids show increased light absorption intensity and range. This work provides a new concept that MOF–rGO hybrids can be used as high performance photocatalysts and applied in the field of environmental protection.