Amorphous Ga2O3 (a-Ga2O3) has attracted extensive attention due to its simple preparation process and low cost, but the extension of photoelectron lifetime caused by the trap state inhibits the responsiveness of a-Ga2O3 photodetector (PD), and how to improve the ultraviolet (UV) gain of a-Ga2O3 based PD is still a challenge. In this study, an a-Ga2O3/ZnO heterojunction PD based on metal-semiconductor-metal (MSM) structure was designed and fabricated by radio frequency magnetron sputtering (RFMS), and a high-concentration electron transport channel was formed by using carrier multiplication and specific band structure in the high-field region of MSM structure, which achieved high optical gain and extraordinary optical detection ability. In the UVC-UVA band, the device has a peak responsivity of 1.59 A W−1 and a high light-dark ratio, EQE and D* of 1×104, 647 % and 3.6×1012 Jones under 5 V, respectively. In particular, compared to ZnO PD and a-Ga2O3 PD, the responsivity of the device is improved by a factor of 21 and 90, respectively. This study provides a new and effective method for the significant improvement of a-Ga2O3 based UV photoelectric detection performance.