We report the design, synthesis, and characterization of a novel heterojunction array of α-Fe(2)O(3)/graphene/BiV(1-x)Mo(x)O(4) core/shell nanorod for photoelectrochemical water splitting. The heterojunction array was prepared by hydrothermal deposition of α-Fe(2)O(3) nanorods onto Ti substrate, with subsequent coating of graphene interlayer and BiV(1-x)Mo(x)O(4) shell by photocatalytic reduction and a spin-coating approach, respectively. The heterojunction yielded a pronounced photocurrent density of ∼1.97 mA/cm(2) at 1.0 V vs Ag/AgCl and a high photoconversion efficiency of ∼0.53% at -0.04 V vs Ag/AgCl under the irradiation of a Xe lamp. The improved photoelectrochemical properties benefited from (1) the enhanced light absorption due to behavior of the "window effect" between the α-Fe(2)O(3) cores and BiV(1-x)Mo(x)O(4) shells, and (2) the improved separation of photogenerated carriers at the α-Fe(2)O(3) nanorod/graphene/BiV(1-x)Mo(x)O(4) interfaces. Our results demonstrate the advantages of the novel graphene-mediated core/shell heterojunction array and provide a valuable insight for the further development of such materials.