Many studies have been conducted regarding the separation behavior of carriers (electrons and holes) because of involving the generation of superoxide radicals (O-2(-center dot), hydroxyl radicals (HO center dot), and hydrogen peroxide (H2O2) in the photocatalytic process of heteropolyacids. Instead, relatively little attention has been focused on the potential Coulomb interactions between photogenerated electrons (e(-)) and holes (h(+)). Herein, choline-phosphotungstic acid (Ch(3)-HPW) was synthesized via one-step acid-base neutralization reaction method, and characterized. The electronic excited state analysis of Ch(3)-HPW showed that the formation of singlet oxygen (O-1(2)) was related to the electron-hole interactions in the photocatalytic process of ground state molecular oxygen (O-3(2)) activation. Subsequently, a facile fuel photocatalytic oxidative desulfurization and extraction system was established on the basis of Ch(3)-HPW, air, and acetonitrile (MeCN), to better understand the O-3(2) activation in specific applications. The main photocatalytic reaction conditions affecting the desulfurization process, including the amount of Ch(3)-HPW, the volume ratio of MeCN to model oil, the initial S-concentration, air/N-2 bubbling, sulfur compounds, and fuel composition, were systematically investigated under UV radiation. The sulfur removal for model oil and straight-run gasoline in the system were 99.6% and 89.9%, respectively. The results of radical scavenger experiments, electron spin-resonance (ESR) spectroscopy, and density functional theory (DFT) calculations further demonstrated that O-1(2), H2O2, and h(+) played important roles in the oxidation of sulfur-containing compounds. A new method was developed for the desulfurization of liquid fuels using green and inexpensive O-2 in this work to promote the development of photocatalytic process of exciton-involved HPA-based photocatalysts.