Intricate ZnO nanorod networks grown on alpha-Fe2O3-coated Si substrate were synthesized by low-temperature solution synthesis method. The obtained samples and alpha-Fe2O3 thin film were characterized by Field Emission Scanning Electron Microscope and X-ray diffraction. The results show that the polar-surface of the (110) preferred orientation of alpha-Fe2O3 thin film is inclined to the Si substrate, which plays a critical role in the formation of the intricate ZnO nanorod networks. The schematic diagram for the formation process of the intricate ZnO nanorod networks has also been proposed. Furthermore, its photoluminescence displays a pronounced UV and green emission.