We have investigated the electronic structure of the interface formed by depositing Au on Cs -doped and Na -doped tris(8-hydroxyquinoline) aluminum (Alq) film using ultraviolet and X-ray photoemission spectroscopy (UPS and XPS). The initial Au deposition quenches the Al q gap state caused by the alkali metal doping. Further Au depositions shift gradually the energy levels opposite to that induced by Cs doping, especially the highest occupied molecular orbital (HOMO) that shows approximately full recovery to the pristine Al q position. However, the recovery is only partial for other levels, most noticeably the C 1s core level. The results indicate that the gap state and energy level positions can be decoupled in the organic semiconductors, and that it is possible to fine tune the electronic structure by selective doping in the interface region.