The polycrystalline VOPc films in phase ii have been fabricated on an indium-tin-oxide-glass substrate. X-ray diffraction pattern and visible absorption spectrum have been used to characterize the packing structure of VOPc molecules. The photovoltaic action spectrum of Al/vanadyl phthalocyanine (in phase II)/indium-tin-oxide (Al/VOPc/ITO) sandwich cell under different modulation frequencies of illuminating light have been measured. The VOPc film acts as a p-type semiconductor. The photovoltage is mainly generated at the Al/VOPc interface. The charge transfer excitons and Frenkel excitons have been revealed by electric modulation reflective spectroscopic technique, both of them may play an important role in the photovoltaic process.