Combined high catalytic activity and thermal stability were achieved with a well-structured, surfactant-free Pd@porous SiO2 yolk-shell nanostructure, resulting from the entirely exposed Pd core particles and highly porous silica shells. Pd@SiO2 core-shell nanoparticles were synthesized by a water-in-oil microemulsion method for direct silica coating of as-prepared tiny Pd nanoparticles. Hydrothermal etching and subsequent high thermal treatment generated large pores in the silica shells and facilitated complete removal of surfactants around the core particles. The surfactant-free Pd@pSiO(2) yolk-shell nanoparticles efficiently catalyzed the oxidation of benzyl alcohol as well as that of various substituted benzyl alcohols.