We modify ZnO nanorods with Zn-porphyrin to obtain the improved characteristics of energy transfer, which is further investigated for the applicability to photovoltaic devices. A nitrogen heterocyclic ligand containing a thiol group is covalently grafted onto the surface of finely structured ZnO nanorods with a length of 50-250 nm and a diameter of 15-20 nm. Zn-porphyrin is then attached to the ligand molecules by the mechanism of metalligand axial coordination. The resulting energy band diagram suggests that the porphyrin-modified ZnO nanorods might provide an efficient pathway for energy transfer upon being applied to photovoltaic devices.