The formation of mesoscopically ordered silica/surfactant composites under alkaline synthesis conditions has been studied by time-resolved in situ small-angle X-ray diffraction with synchrotron radiation. Alkyltrimethylammoniumbromide surfactants, C(n)()TAB, of different chain lengths (n = 14, 16, and 18) as well as mixtures thereof were used as structure directing agents and the measurements were carried out at two different temperatures. A linear relationship between the mean surfactant chain length and the d spacing of the hexagonal phase was observed, suggesting an ideal mixing of the surfactants in the supramolecular surfactant aggregates. It is shown that the formation of the hexagonal phase is kinetically controlled mainly by the rate of silicate condensation, while the effect of changes in the surfactant chain length on the kinetics is small under the studied conditions. Two concominant, albeit partly interlinked, processes, suggested being intra- and intermicellar condensation, followed by aggregate-aggregate condensation, govern the nucleation and growth of the hexagonal phase. The two-step mechanism is confirmed by a microcalorimetric study where the heat evolved during the hydrolysis-condensation reactions is followed as a function of time.