In this work, we report a generic method of reverse microemulsion for syntheses of uniform and well-dispersed hollow porous silica nanospheres with metal (oxide) nanoparticles inside their cavities (MxOy@HPSNs or M@HPSNs), where the water phase consists of poly(ethylene imine) stabilized metal hydroxide nanoaggregates. During silica deposition, the mentioned nanoaggregates function as void templates as well as a platform to deliver catalytic functionality into voids. The subsequent calcination simultaneously gives hollow nanostructures and metal (oxide) nanoparticles inside central voids. The method applies to the metals that have hydroxide precipitates at basic conditions, and is suitable for most of catalytically active metals. As a demonstration, Pd@HPSNs illustrate high catalytic efficiency for selective hydrogenation of phenylacetylene at ambient H2 pressure, and the enhancement could be assigned to the effect of void confinement.