Poly(vinylbenzyl chloride), (PVBC) latex particles of about 100 nm in size are prepared by emulsion polymerization. Silyl functional groups are introduced onto the PVBC-nanoparticle templates via surface-initiated atom transfer radical polymerization of 3-(trimethoxysilyl)propyl methacrylate. The silyl groups are then converted into a silica shell, approximately 20 nm thick, via a reaction with tetraethoxysilane in ethanolic ammonia. Hollow silica nanospheres are finally generated by thermal decomposition of the PVBC template cores. Field-emission scanning electron microscopy and field-emission transmission electron microscopy are used to characterize the intermediate products and the hollow nanospheres. Fourier-transform infrared spectroscopy results indicate that the polymer cores are completely decomposed.