Volatile organic compounds (VOCs), including benzene, toluene, and formaldehyde, are hazardous air pollutants that require efficient and sustainable mitigation strategies. Photocatalytic degradation of VOCs offers a promising pathway; however, its performance is strongly influenced by multiple operational parameters. Here, we present a systematic investigation of toluene degradation under ultraviolet-C (UVC) irradiation across controlled temperatures using Ga₂O₃ as a photocatalyst. A comprehensive analysis revealed that elevated temperatures enhanced photocatalytic activity by accelerating chemical reaction rates. However, further temperature increases led to a decrease in performance due to a reduction in the reactant adsorption rate. An optimal operating temperature was identified, at which the balance between chemical reaction rates and reactant adsorption yields the highest degradation efficiency. These findings demonstrate Ga₂O₃ as a promising photocatalyst and provide fundamental insights into the temperature-dependent photocatalytic mechanisms governing VOC removal in practical environmental applications.