We report on a new strategy to synthesize asymmetrical hollow colloidal particles by exploiting limited chemical diffusion that occurs at the periphery of a solvated polymer brush on the particle surface. The polymer brush-in our case poly(glycidyl methacrylate)-bears hydroxyl groups upon hydrolysis and is partially cross-linked under the Stöber condition of silication. Desolvation of the polymers creates a cavity. While elucidating this new mechanism, we demonstrate that particles with various types of cavities and tunable properties can be synthesized, including the ones bearing hemispherical and crescent shapes, as well as particles with wrinkled surfaces. Furthermore, we show that the hollow particles adopt preferred orientations because of their shape and composition attributes, which is further explored to facilitate the confined synthesis of nanocrystals.