Mesoporous Ce-doped Pd nanospheres with a hollow chamber are synthesized by chemical reduction of PdCl2 with KBH4 in an aqueous solution containing Ce(NO3)3 and Bu4PBr. The later acts as a template for the hollow chamber via forming organic vesicles. During the liquid-phase phenol hydrogenation to cyclohexanone, the as-prepared catalyst exhibits a much-higher activity than the corresponding solid nanoparticle catalyst prepared in the absence of Bu4PBr. Meanwhile, the Ce dopants greatly enhance the activity and selectivity to cyclohexanone. The hollow chamber is quite stable against heating in solution and the catalyst could be used repetitively many times. Such a catalyst shows a good potential in industrial applications.