While organically bridged alkoxysilane precursors such as bis(triethoxysilyl)ethane (BTESE) find increasing use in materials synthesis, their polymerization still has not been subject to detailed kinetic investigations. One factor complicating the measurement and interpretation of the behavior of these monomers is their tendency to aggregate during polymerization into small clusters or particles. Here, the phase behavior and kinetics of BTESE during polymerization in acidic water-ethanol solutions are investigated in situ using (29)Si NMR spectroscopy. Based on macroscopic observation of the colloidal stability of the reacting solutions, a ternary pseudo-phase diagram is constructed and solutions that seem from a macroscopic point of view to be favorable for kinetic investigation are probed in situ using (29)Si NMR. However, even when the solutions remain optically clear, the polymerization mixtures are sometimes prone to gradual loss of NMR signal. The rate of signal loss is found to be dependent on the initial composition as well as the pH of the reacting mixtures. We speculate that this phenomenon is caused by microphase separation of reaction intermediates formed early in the polymerization process. This phenomenon is likely to affect the formation and distribution of oligomers in the solution that eventually react together to form a material. (C) 2011 Elsevier Inc. All rights reserved.