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Gallium Oxide is a promising material for power device applications. We focused on corundum structured gallium oxide (α-Ga2O3) and α-(AlxGa1-x)2O3/ α-Ga2O3 heterostructure devices. We prepared α-(AlxGa1-x)2O3 alloy and these laminate structures on c-plane sapphire substrates. The band offset of the α-Ga2O3/α-(AlxGa1-x)2O3 heterostructure was measured by X-ray photoelectron spectroscopy (XPS). The band alignment was estimated to be type I with very narrow valence-band offset energy.