The structure and formation kinetics of organic/silica hybrid species prepared from acid hydrolysis of vinyltriethoxisilane has been studied in situ by small-angle X-ray scattering (SAXS) at 298, 318, and 333 K in a strongly basic step of the process. The evolution of the SAXS intensity is compatible with the formation of linear chains which grow, coil, and branch to form polymeric macromolecules in solution. The SAXS data were analyzed by the scattering from a persistent chain model for polymeric macromolecules in solution using a modified branching Sharp and Bloomfield global function, which incorporates a branching probability typical of randomly and nonrandomly branched polycondensates, and in a particular case, it is also valid for polydisperse coils of linear chains. Growth of linear chains and coiling dominate the process up to the formation of likely monodisperse Gaussian coils or polydisperse coils of linear chains. The link probability to form a branching point is increased with time to form nonrandomly branched polycondensates in solution. The kinetics of the process is accelerated with temperature, but all the curves formed by the time evolution of the structural parameters in all temperatures can correspondingly be matched on a unique curve by using an appropriate time scaling factor. The activation energy of the process was evaluated as Delta E = 21 +/- 1 kJ/mol. The characteristics of the kinetics are in favor of a complex overall mechanism controlled by both condensation reactions and dynamical forces driven by interfacial energy up to the final structure development of the hybrids.