High-performance Ga2O3 solar-blind photodetectors are critical for applications due to their selective solar-blind ultraviolet sensitivity. The quality of the Ga2O3 film has a significant impact on the performance of photodetectors. This study presents an innovative approach to enhancing the quality of Ga2O3 films through the introduction of a naturally graded buffer layer, which is formed by the oxidation of a metallic Ga film and significantly improves interface stability by accommodating lattice mismatches and reducing defects. The structural and compositional characteristics of Ga2O3 films were comprehensively analyzed using UV–vis (ultraviolet–visible) spectroscopy, AFM (Atomic Force Microscope), PL (Photoluminescence Spectroscopy), TEM (Transmission Electron Microscope), and XPS (X-ray Photoelectron Spectroscopy). The photodetectors fabricated from these films demonstrate responsivity of 99.8 mA/W and a solar-blind UV/UV ratio of 1.17 × 103, with significant improvement compared to direct deposited films. This research highlights the potential of natural buffering layers to advance the performance of Ga2O3-based solar-blind UV detectors.