AbstractThis article investigates the ultrahigh sensitivity and DUV photodetection capability of a hybrid oxide‐nitride stack comprising β‐Ga₂O₃ layers grown heterogeneously on a conductive ceramic crystal. The ceramic crystal, namely a TiN interlayer, which acts as a lattice template, was heteroepitaxially grown on bulk MgO. Because β‐Ga₂O₃ is a monoclinic phase crystal, it is conjectured that its nucleation and growth process on cubic phase TiN is entropic in nature, whereby the two unit cell configurations of the β‐Ga₂O₃ crystal, exhibiting rotational twin domains, grew alternately side by side in a semiperiodic manner on TiN while maintaining a single crystal phase. This film formation mechanism contributed to the introduction of additional defects in the β‐Ga₂O₃ lattice (Taylor's dislocations in addition to growth‐induced vacancies). The fabricated DUV photodetectors based on the resulting metal‐semiconductor junction heterodiodes exhibited an average peak spectral responsivity of 276.72 A W⁻¹ and fast decay constants in the order of 500 ms in the ultraviolet‐C regime, with true solar‐blind characteristics manifested by ultraviolet‐to‐visible rejection ratios of up to 2 × 10³ and illuminating power density of around 70 μW cm⁻². The crystallographic orientation relationships between the TiN and β‐Ga₂O₃ crystals, as well as the lattice fit and dislocation types, are revealed and examined.