Owing to the fast response speed and low energy consumption, photovoltaic vacuum-ultraviolet (VUV) photodetectors show prominent advantages in the field of space science, high-energy physics, and electronics industry. For photovoltaic devices, it is imperative to boost their open-circuit voltage, which is the most direct indicator to measure the photoelectric conversion capability. In this report, a quasi-Fermi level splitting enhanced effect under illumination, benefiting from the variable Fermi level of graphene, is proposed to significantly increase the potential difference up to 2.45 V between the two ends of p-Gr/i-AlN/n-SiC heterojunction photovoltaic device. In addition, the highest external quantum efficiency of 56.1% (under the VUV irradiation of 172 nm) at 0 V bias and the ultra-fast photoresponse of 45 ns further demonstrate the superiority of high-open-circuit-voltage devices. The proposed device design strategy and the adopted effect provide a referential way for the construction of various photovoltaic devices.