TiO2-C materials have been prepared by solvothermal and slurry synthesis and the influence of carbon properties upon the catalytic activity and selectivity of Pd-based catalysts on phenol hydrogenation in aqueous phase under mild reaction conditions has been studied. The nature of the catalysts can be modified to direct the reaction either to cyclohexanol (similar to 100% yield) or to cyclohexanone (similar to 96% yield). High selectivity to cyclohexanone is obtained with Pd on more polar TiO2-C supports, while when these are transformed into hydrophobic TiO2-C supports the resultant catalyst becomes selective to cyclohexanol. Thus, product distribution during the selective phenol hydrogenation in aqueous phase is easily controlled by controlling the functionalization of the hybrid support. (C) 2011 Elsevier B.V. All rights reserved.