Solvent effects are important for the solution preparation of nanoscale metal materials, in which the sizes and properties of the nanomaterials are greatly influenced by the solvents. In this study, a series of Pd/XC-72 catalysts were synthesized by a facile solvothermal method in solvents with different numbers of hydroxyl groups, including ethanol, ethylene glycol, and glycerine. The as-prepared catalysts Pd/XC-72(EA), Pd/XC-72(EG) and Pd/XC-72(GI) were characterized by XRD, TEM, TGA, ICP-MS and multipoint nitrogen adsorption-desorption experiments. It was found that Pd/XC-72(GI) had the highest metallic dispersion and the smallest particle size (4.9 nm). Furthermore, Pd/XC-72(GI) exhibited the best catalytic performance for solvent-free selective oxidation of benzyl alcohol while the catalytic activities of Pd/XC-72 catalysts decreased in the order: Pd/XC-72(GI) > Pd/XC-72(EG) > Pd/XC-72(EA).