The effect of coating Ru particles with a film of hydrophilic materials on the tetra-phase partial hydrogenation of benzene to cyclohexene was examined. By the sol gel method, amorphous mesoporous TiO2, ZrO2, and SiO2 were coated on hexagonal Ru particles, by which Ru@XO2 (X = Ti, Zr or Si) catalysts were prepared. During the partial hydrogenation of benzene on Ru@XO2, the diffusion of benzene and cyclohexene dissolved in the water phase onto Ru particles is suppressed by the presence of mesoporous coating film. The diffusion of benzene is retarded further by the hydrogen bonding with the structural OH group& contained in hydrophilic materials. Because of the delicate diffusion behavior of benzene and cyclohexene through coating film, a decreasing rate of benzene conversion but a significantly increasing cyclohexene selectivity was observed in the partial hydrogenation on different Ru@XO2 catalysts. A maximum cyclohexene yield of 52.6 mol % occurs on Ru@TiO2 at the benzene conversion of 85.0%.