The first example of biomimetic siloxane bond formation catalyzed by molecularly imprinted polymers (MIPs) is reported. MIPs were prepared by free-radical polymerization and characterized via a combination of solid-state NMR, infrared spectroscopy, and electron microscopy studies. Methacrylic acid-based polymers with high functional monomer content were observed to catalyze the hydrolysis and condensation of a model monoalkoxysilane to a greater extent when compared with the corresponding blank (non-imprinted) materials and buffer control solutions, as judged by quantitative gas chromatography investigations. Moreover, the polymers were used as biomimetic catalysts to synthesize silica-MIP hybrids with a certain degree of control of the microstructure of the resulting composites. (C) 2011 Elsevier Inc. All rights reserved.