Recently, hollow spheres have attracted increasing interest because of their application in drug delivery, [1][2][3] cell and enzyme transplantation, [4] gene therapy, [5] separation in biomedicine, and as contrast agents in diagnostics. [6,7] Despite significant advances in the preparation of hollow inorganic or polymeric spheres, [8][9][10][11] the construction of nanosized hybrid hollow spheres with both inorganic component and organic polymers as the shells remains a major challenge. Currently, a widely used approach for the synthesis of hybrid micro or submicron hollow spheres is the core-template-based strategy in which the inorganic components are coated on the polymer particles by sol-gel chemistry [12] or layer-by-layer deposition. [13] One advantage of such an approach is that the thickness of the coating layers is controllable. Although successful in the preparation of hollow hybrid spheres, the core-template-based approach faces limitations involving the selection in core composition and nanosized core templates. Furthermore, the core must be removed to create the hollow center. Hence, a core-template-free strategy for the production of hollow hybrid spheres is of particular interest. Previous efforts towards the preparation of hollow hybrid spheres with micrometer dimensions and in the absence of a core template include the assembly of inorganic nanoparticles into hollow spheres by using block copolymers, [14] the