Substrate effect on energy level alignment of CH3NH3PbI3 are studied. CH3NH3PbI3 perovskite films reveal strong N-type property. CH3NH3PbI3 LUMO is pined at Fermi level of low WF electrodes. Interfacial electronic structure at CH3NH3PbI3-MoO3 interfaces are discussed. Efficient hole extraction layer is critical important for CH3NH3PbI3 solar cell.