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p-type Cr2MnO4 with bandgap 3.01 eV was sputter deposited onto (2¯01) and (001) n-type or semi-insulating β-Ga2O3.The heterojunction of p-type CrMnO4 on n-type Ga2O3 is found to be type II, staggered gap, i.e., the band offsets are such that both the conduction and valence band edges of Ga2O3 are lower in energy than those of the Cr2MnO4. This creates a staggered band alignment, which can facilitate the separation of photogenerated electron-hole pairs. The valence band edge of Cr2MnO4 is higher than that of Ga2O3 by 1.82–1.93 eV depending on substrate orientation and doping, which means that holes in Cr2MnO4 would have a lower energy barrier to overcome to move into Ga2O3. Conversely, the conduction band edge of Cr2MnO4 is higher than that of Ga2O3 by 0.13–0.30 eV depending on substrate doping and orientation, which would create a barrier for electrons in Ga2O3 to move into Cr2MnO4. This heterojunction looks highly promising for p-n junction formation for advanced Ga2O3-based power rectifiers.