Carbon black (CB)-supported Pd catalysts (Pd/CB) were covered with organosilica layers via the hydrolysis of phenyl-triethoxysilane (PhTES). Coverage of Pd nanoparticles with organosilica layers suppressed particle sintering of Pd, as compared to the case of uncovered Pd/CB. The organosilica layers had hydrophobic properties because of the presence of phenyl groups. As a result, the organosilica-coated Pd catalysts prepared using PhTES showed superior catalytic performance for cyclohexane dehydrogenation, even after reduction at 623 K under H-2 atmosphere.