The solar-blind photodetectors (SBPDs) based on the wide-bandgap semiconductor gallium oxide (Ga2O3) exhibit significant potential for applications in military, civilian, and medical fields. Although multiple structural designs of Ga2O3-based SBPDs have been proposed, their performance typically falls short of commercial standards. However, the photoresponse speed of most self-powered PDs decreases rapidly in the solar-blind region. To address this issue, we first prepared high-quality single-crystal β-Ga2O3 films using RF magnetron sputtering, which exhibit an average transmittance exceeding 85% across the 400–800 nm range and possess a relatively smooth surface. Subsequently, a superior performance self-powered SBPD of vertical structure of n-Si/n-Ga2O3/p-Li:NiO dual-junction was fabricated, which possesses a responsivity of 0.18 mA/W, a photo-to-dark current ratio of 395, rapid rise/decay times of 132/148 ms, and a specific detectivity of 1.57 × 109 Jones at 0 V bias under 254 nm illumination. The photocurrent of the device fully recovered to its initial level after experiencing changes in ambient temperature [from room temperature (RT) to 100 °C and back to RT], demonstrating robust stability in harsh environments. In addition, the valence band structures of p-Li:NiO and n-Ga2O3 were investigated in detail using XPS, and the working mechanism of the devices was analyzed based on the Fermi level alignment. The excellent performance of PDs can be attributed to the increased depletion layer width, which generates more photogenerated carriers. Additionally, the separation and transmission of photo-induced carriers are enhanced by the superposition of a double built-in electric field. Our strategy offers a promising approach for achieving high-performance Ga2O3-based photovoltaic PDs.