Interfacial properties of perovskite layers and metal electrodes play a crucial role in device performance and long-term stability of perovskite solar cells. In this work, we performed a comprehensive study of the interfacial structures and ion migration at the interface of a CH3NH3PbI3 perovskite layer and an Al electrode using in situ synchrotron radiation photoemission spectroscopy measurements. It was found that the Al electrode can react with the perovskite layers, leading to the formation of aluminum iodide species and the bonding between Al and N, as well as the reduction of Pb2+ ions to metallic Pb species at the interface. Moreover, during the Al deposition, iodide ions can migrate from the CH3NH3PbI3 subsurface to the Al electrode, while the reduced Pb remains at the subsurface. The depth profile photoemission measurements, made by varying the photon energies of incident synchrotron radiation X-rays, demonstrate that the reaction occurs at the Al/CH3NH3PbI3 interface at least with a thickness of ∼3.5 nm below the perovskite surface. This study provides an atomic-level fundamental understanding of the Al/CH3NH3PbI3 interfacial structures and insight into the degradation mechanisms of perovskite solar cells when using Al metal as the electrode.