The band alignment of Al2O3/n-Ga2O3 was investigated by x-ray photoelectron spectroscopy (XPS). With a band gap of 6.8 ± 0.2 eV measured for Al2O3, the conduction and valence band offsets at the interface were estimated to be 1.5 ± 0.2 eV and 0.7 ± 0.2 eV, respectively. The conduction band offset was also obtained from tunneling current in Al2O3/n-Ga2O3 (2¯01) metal-oxide-semiconductor (MOS) diodes using the Fowler-Nordheim model. The electrically extracted value was in good agreement with the XPS data. Furthermore, the MOS diodes exhibited small capacitance-voltage hysteresis loops, indicating the successful engineering of a high-quality Al2O3/Ga2O3 interface.