Hollow silica nanoparticles can be spontaneously generated without a template on the basis of the porous nature of silica and the high surface energy on the nanometer scale. We show that solid silica particles synthesized by the Stober and microemulsion methods initially develop small pores inside the nanoparticles under slightly basic conditions as a result of base-catalyzed etching. With further reaction, those small seed pores merge into a single void to reduce the surface energy of small pores, generating well-defined hollow nanoparticles. This behavior is unique to nanometersized porous materials, and the shape evolution is size-dependent, reinforcing the importance of evaluating the reactivity and structural changes of nanomaterials as well as their physical properties in different size ranges. The mechanism described here provides a simple way to generate uniform hollow nanoparticles of porous materials.