Interesting of polymer capsules is increasing in various fields, including synthetic chemistry, biotechnology and pharmaceutics. Currently, there is an increased focus on the synthesis and examination of nanoporous materials with hierarchical nanostructures because they can exhibit the advantages of each of hierarchical pores with a synergistic effect. In this work, porous hollow nanoparticles were prepared using colloidal silica (CS). The nanoparticles were prepared by initially coating silica with 3-methacryloxypropyltrimethoxysilane (MPS) and forming a shell by the polymerization of a mixture of styrene and methyl vinyl ketone (MVK) with divinylbenzene (DVB), followed by the removal of silica core by etching with hydrofluoric acid. The resulting polymeric shell was then formed porous structures by photodegrading poly(MVK) components with ultraviolet (UV) irradiation.