We investigated the electronic structure and the energy level alignment at the interfaces between perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) and metals (Au, Cu and Co) by ultraviolet photoelectron spectroscopy (UPS). In the case of PTCDA/Au interface, the apparent interface states and charge transfer (CT) states were not observed in its UPS spectra. In the case of PTCDA/Cu and Co interfaces, however, we found that the CT from metal to PTCDA occurred, and that the apparent CT states were observed at PTCDA/Cu interface.