Abstract Implementing high‐performance ultraviolet C photodetectors (UVC PDs) based on β‐Ga 2 O 3 films is challenging owing to the anisotropic crystal symmetry between the epitaxial films and substrates. In this study, highly enhanced state‐of‐the‐art photoelectrical performance is achieved using single‐domain epitaxy of monoclinic β‐Ga 2 O 3 films on a hexagonal sapphire substrate. Unlike 3D β‐Ga 2 O 3 films with twin domains, 2D β‐Ga 2 O 3 films exhibit a single domain with a smooth surface and low concentration of point defects, which enable efficient charge separation by suppressing boundary‐induced recombination. Furthermore, a tailored anti‐reflection coating (ARC) is adopted as a light‐absorbing medium to improve charge generation. The tailored nanostructure, which features a gradient refractive index, not only substantially reduces the reflection, but also suppresses the surface leakage current as a passivation layer. This study provides fundamental insights into the single‐domain epitaxy of β‐Ga 2 O 3 films and the application of ARC for the development of high‐performance UVC PDs.