Interfacial band offset and band bending of organic semiconductors are critical to understand and improve organic photovoltaic cells. In this study, the energy level alignment of fullerene(C60) / metal-free phthalocyanine (H2Pc) interface which is one of the model interfaces of organic photovoltaic cells has been investigated using UV and X-ray photoemissions. For both ‘H2Pc on C60’ and “C60 on H2Pc' interfaces, 0.3 eV downward energy level shift was observed in XPS at the interface formation. This energy shift is quite steep in contrast to the band bending observed for C60/metal interfaces in our previous study, where thickness of 500nm was required to achieve 0.21eV band bending to get Fermi level alignment between metal electrode and C60. To clarify the origin of the band bending, the effect of the insertion of C60-H2Pc co-deposited layer between C60 and H2Pc layers was also investigated. The result suggested that possible doping of H2Pc to C60 is not main origin of the observed energy shift. We also found that the vacuum level shift at H2Pc/C60 interface is strongly dependent on the deposition sequence of the interface formation.