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We used ultraviolet photoelectron spectroscopy (UPS) to study the electronic structure at the interface between organic semiconductor (CBP) and metals (Mg, Ag, and Au). Controlling the injection of charges at the interface requires a better understanding of the basic mechanism of the formation of interface states. In this context, photoelectron spectroscopy and density functional theory calculations were used to investigate the interaction of CBP with metal (111) surfaces. The position of HOMO relative to the Fermi level and the magnitude of the interface dipole were measured for each interface by UPS measurement. For CBP on Au, interface state (continuous state) was observed near the Fermi level by density functional theory calculations. However, no interface state was observed for CBP on Mg and Ag. It is suggested that the interface state plays an important role in charge transport at the interface. It was analyzed by density functional theory calculations that the interface state is formed due to interaction of CBP with metals and the position of the Fermi level varies strongly with the metal work function. The mechanism of formation of interface states and electrical properties were discussed.