This work is focused in a systematic study of hydrocarbon reactivity in molecules with C-H bonds with different hybridization, in reaction of photocatalytic oxofunctionalization under visible light irradiation and room temperature and pressure. For this purpose, where synthesized and characterized five titanium dioxide-based and three bismuth oxyhalide-based photocatalysts. In the cyclohexane oxofunctionalization, titanium dioxide-based photocatalysts show higher cyclohexanone selectivity than bismuth oxyhalide-based photocatalysts. In all studied systems only cyclohexyloxy radical was observed as an intermediary in the early stages of the cyclohexane oxofunctionalization reaction. Nevertheless, the generation of hydroxyl radicals was evidenced, only when BiOI was used as photocatalyst. In this way, the hydroxyl radical production ability of this material was associated to the higher selectivity of this material for cyclohexanol production. On the other hand, there are reports which suggest that the selectivity of photocatalytic process may be modulated through the tuning of structural parameters of semiconductor photocatalysts as the preferential exposition of certain crystalline facets. In the present work, a linear dependence of cyclohexanol/cyclohexanone ratio obtained in photocatalytic oxofunctionalization of cyclohexane by BiOI under visible light irradiation on the (1 1 0)/(0 0 1) intensity ratio of BiOI photocatalyst was established. Finally, the cyclohexanol and cyclohexanone yields of photocatalytic oxofunctionalization of cyclohexane in acetonitrile catalyzed by the commercial photocatalyst TiO2 Degussa P25, were optimized by a response surface model. Besides, the irradiation source effect on photocatalytic conversion of cyclohexane was studied through comparison of yield attained when this reaction was performed under metal halide lamp and with direct solar irradiations.PFCHA-BecasPFCHA-Becas