A vertically aligned array of ZnO nanorods, fabricated on conductive ITO substrate in aqueous solution, was characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), and UV–visible transmission spectroscopy. Surface photovoltage (SPV) techniques based on a lock-in amplifier and a Kelvin probe were both employed to study the photogenerated charges in the system. The effects of ethanol solvent and a liquid-crystalline porphyrin, [5-(para-dodecyloxy)phenyl-10,15,20-tri-phenyl] porphyrin (DPTPP), on the photovoltage enhancement in the ZnO nanorod array were studied via SPV comparison between different irradiation directions on the system. We demonstrate that the ethanol adsorption could induce the space charge region to expand towards the ZnO/ITO interface. In the absence of ethanol, the ZnO nanorod array with the DPTPP adsorption showed enhanced SPV with reduced attenuation rate of photogenerated charge carriers. We found that the separation of photogenerated charges could be further improved by coating the surface with DPTPP and ethanol together. Furthermore, the SPV spectra patterns of the composite system with opposite incident-light directions reveal that the DPTPP molecules adsorbed just at the surface of ZnO nanorods adopt a more monomeric alignment in contrast to the aggregative state in the DPTPP bulk.