Preliminary results were previously reported indicating that uniform, hollow silica–aerogel spheres of controlled size and thickness can be fabricated by controlled hydrolysis and condensation of tetraethylorthosilicate (TEOS). The method consists of first producing a stream of hollow drops of a mixture of TEOS, H2O, ethanol, and a catalyst using a dual‐nozzle system and then introducing the drops into a gelation chamber where the drops solidify into a rigid form while being levitated by a gelation gas mixture. A detailed further study designed to understand and control the kinetics of the sol–gel processing that is responsible for the hollow silica–aerogel sphere formation is described. Specifically, the optimal rheology and stoichiometry of the reactant solution, the make‐up of the gelation/levitation gas mixture, and the characteristics of the resulting silica–aerogel spheres, such as the size, thickness, porosity, pore size, and density, are investigated.