Tris(8-hydroxyquinoline) aluminum (Alq3) based organic light emission diodes (OLED) have been a focus of material research in recent years. One of the key issues in searching for a better device performance and fabricating conditions is suitable electron-injection materials. We have investigated the energy alignment and the interface formation between different metals and Alq3 using X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS). The interface is formed by depositing the target cathode material, such as Ca, Al or Al/LiF, onto an Alq3 film in a stepwise fashion in an ultrahigh vacuum environment. While the UPS results show the work function and vacuum level changes during interfaces formation, implying a possible surface dipole layer, XPS results show a more detailed and complex behavior. When a low work function metal such as Ca is deposited onto an Alq3 surface, a gap state is observed in UPS. At the same time, a new peak can be observed in the N 1s core level at a lower binding energy. These results can be characterized as charge transfer from the low work function metal to Alq3. The shifting of core levels are also observed, which may be explained by doping from metal atoms or charge diffusion. These interfaces are drastically different than the Al/Alq3 interface, which has very poor electron injection. At the Al/Alq3 interface there is a destructive chemical reaction and much smaller core level shifts are observed. Based on detailed analysis, energy level diagrams at the interface are proposed.