Since photocatalytic reactions are almost consistent with the concept of green chemistry, substance conversion using photocatalysts has recently attracted the attention of researchers in the fields of organic chemistry, physical chemistry and material chemistry. We investigated photoinduced ring hydrogenation of phenol over a metal-loaded titanium(IV) oxide (TiO2) photocatalyst without the use of H-2 gas and we report here the effects of various parameters, including the type and amount of metal co-catalyst loaded on TiO2 and the kinds of solvents and hole scavengers, on the ring hydrogenation. We found that the combination of an Rh co-catalyst, water and oxalic acid resulted in the highest yield of cyclohexanol. Detailed analyses revealed that phenol was first hydrogenated to cyclohexanone via keto-enol tautomerism of cyclohexenol followed by hydrogenation of cyclohexanone to cyclohexanol and that adsorption of phenol onto Rh-TiO2 is a factor of great importance for the ring hydrogenation.