Surface-initiated living free-radical polymerization is employed in a multistep procedure to prepare hollow polymeric nanocapsules. Initially, trichlorosilyl-substituted alkoxyamine initiating groups are attached to the surface silanol groups of silica nanoparticles. This surface layer of initiating groups is then used to grow functionalized linear chains leading to a core-shell morphology. The choice of functional groups is governed by their ability to undergo facile crosslinking reactions, with both active ester and benzocyclobutene groups being examined. Under either chemical or thermal conditions, the reaction of these functionalities gives a crosslinked polymeric shell that is covalently attached to, and surrounds, the central silica core. Removal of the silica core with HF then gives the hollow polymeric nanocapsules, which are stable under solvent dissolution and thermal treatment because of their crosslinked structure.