The sustainable transformation of basic chemicals into organic compounds of industrial interest using mild oxidation processes has proved to be challenging. The production of cyclohexanol and cyclohexanone from cyclohexane is of interest to the nylon manufacturing industry. However, the industrial oxidation of cyclohexane is inefficient. Heterogeneous photocatalysis represents an alternative way to synthesize these products, but the optimization of this process is difficult. In this work, the yields of photocatalytic cyclohexane conversion using Degussa P-25 under visible light were optimized. To improve cyclohexanol production, acetonitrile was used as an inert photocatalytic solvent. Experiments showed that the use of the optimized conditions under solar light radiation did not affect the cyclohexanol/cyclohexanone ratio. In addition, the main radical intermediary produced in the reaction was detected by the electronic paramagnetic resonance technique.