Tetramethylorthosilicate (tetramethoxysilane; TMOS), a common sol–gel precursor, is found to undergo spontaneous hydrolysis and condensation reactions in a predominantly chloroform/methacrylic acid solution, i.e., the major components of a traditional molecular imprinted polymer (MIP) recipe, without the addition of water. The formation of the shorter chain alkoxyoligosilanes is monitored by GC–MS and possible mechanisms for their formation are proposed. While the data collected indicates that the classical sol–gel route may explain the formation of the majority of the silicates, a secondary mechanism may also play a role. The finding that TMOS can undergo sol–gel chemistry in this hydrophobic medium may support a novel synthetic strategy for the preparation of hybrid MIPs (HMIPs): the in situ, serial polymerizations of the inorganic and organic components, respectively. Preliminary evidence to support the potential effectiveness of this strategy is presented.