Herein, we report epitaxial growth of p-type Ni doped gallium chromium oxide thin film on Al2O3 substrates and studied its band alignment properties with that of the substrate. Thin films are grown using the magnetron-sputtering technique. Synchrotron-based XRD measurements, performed in the coplanar and non-coplanar geometries, confirm high-quality single domain epitaxial growth of p-type α-GaCrO3:Ni. Pendellosung oscillations around the Bragg peak and transmission electron microscopy reveal the high interfacial quality of p-type α-GaCrO3:Ni films with the substrate. Thin film, thickness ∼200 nm, shows around 70% average transmission. The values of valence band and conduction band offsets are determined to be 2.79 ± 0.2 and 0.51 ± 0.2 eV, respectively, which confirm straddling gap band alignment at the heterojunction. This type of alignment creates a threshold barrier for the selective charge carriers and is useful in enhancing the performance of a wide range of devices, including UV photodetectors, metal oxide semiconductor high electron mobility transistors, and light emitters.