A non-surfactant-based synthesis approach to mesoporous hollow spheres through the use of colloidal silica is presented. Based on nanoparticle assembly chemistry developed previously for silica/polymer hybrid microcapsules, the room-temperature preparation follows a two-step sequence: (1) the electrostatic reaction of cationic polymer with an anionic salt solution, resulting in a suspension of salt-bridged polymer aggregates; and (2) the electrostatic reaction between this suspension and an aqueous suspension of nanoparticles (NPs). As a specific example, 13-nm silica particles, combined with polyallylamine and sodium citrate, gave silica/polymer hollow spheres with a mean diameter of 2.1 μm and a BET surface area of 4 m²/g. After calcination at 600 °C, the resulting silica-only microcapsules had a BET surface area of 259 m²/g, a modal pore size of 4.0 nm, and a pore volume of 0.38 cc/g, values that exceeded those of calcined silica NPs. This colloidal silica-based material is an example of the simultaneous control of pore size (at the nanometer scale) and particle morphology (at the micrometer scale) that is possible through charge-driven NP assembly.