A novel nanocomposite consisting of α-Fe2O3, Mn3O4 and reduced graphene oxide (r-GO) has been facilely synthesized through a two-step method: solvothermal reaction for Mn3O4-modified α-Fe2O3 (α-Fe2O3/Mn3O4) and self-assembly process for combining α-Fe2O3/Mn3O4 with r-GO (α-Fe2O3/Mn3O4/r-GO). The morphology and structure of the nanocomposite were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that rod-like hematite was modified by Mn3O4 and dispersed on the surface of r-GO. Raman and Fourier transform infrared spectra (FTIR) showed superior interfacial contacts between α-Fe2O3/Mn3O4 and r-GO. Ultraviolet-visible diffuse reflectance spectroscopy (DRS) and photoelectrochemical characterization revealed a high light-harvesting efficiency, a lowered overpotential for water oxidation and an excellent charge transfer performance of α-Fe2O3/Mn3O4/r-GO nanocomposite with heterostructures. The photocatalytic oxygen evolution from the optimized photocatalyst was up to 1406.2 μmol g(-1) in 10 h of UV-vis light irradiation and the quantum yield was ca. 4.35% at 365 nm. Our investigation suggests that constructing a catalyst with heterostructures is a promising method to enhance photocatalytic activity.