The polymerization of 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane in ethanol, catalyzed by 0.5, 1.0 and 2.0 M HCl.H2O, has been examined using time-resolved near-IR (NIR) and 2D NIR correlation techniques. The time-resolved NIR results have demonstrated that the growth of polymeric aggregates prior to the phase separation proceeds in a two-step process, which depends upon the HCl concentration. Furthermore, it has been found that the 2D NIR correlation data provide direct information on the sequence of the intricate reaction steps and interaction of participating components through hydrogen bonding in the growth process.