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The organosulfur compounds present in liquid fuels are hazardous for health, asset, and the environment. The photocatalytic desulfurization technique works at ordinary conditions and removes the requirement of hydrogen, as it is an expensive gas, highly explosive, with a broader flammability range and is declared the most hazardous gas within a petroleum refinery, with respect to flammability. The projected work is based on the synthesis of V2O5 microspheres for photocatalytic oxidation for the straight-run diesel (SRD) and diesel oil blend (DOB). The physicochemical properties of V2O5 microspheres were examined by FT-IR, Raman, UV-vis DRS, SEM, and Photoluminescence evaluations. The as-synthesized photocatalyst presented a trivial unit size, a narrow bandgap, appropriate light-capturing capability, and sufficient active sites. The desulfurization study discovered that the anticipated technique is substantial in desulfurizing DOB up to 37% in 180 min using methanol as an interfacing agent. Furthermore, the outcome of employing a range of polar interfacing solvents was examined, and the 2-ethoxyethanol elevated the desulfurization degree up to 51.3%. However, the anticipated technology is constrained for its application in sulfur removal from SRD. Additionally, the mechanism for a photocatalytic reaction was seen in strong agreement with pseudo-first-order kinetics. The investigated photocatalyst exhibited a compromised recyclability and regeneration tendency.