Condensation reactions between tetraethyl orthosilicate and linear aliphatic diol monomers at moderately high temperatures in proper stoichiometric ratios gave crosslinked poly(orthosilicate)s. The synthesized crosslinked polymers were found to be insoluble in common organic solvents, such as tetrahydrofuran, dichloromethane, benzene, and acetone, but did show swelling abilities in these solvents. All of the crosslinked polymers had moderate thermal stability and good, regenerable solvent uptake abilities. The synthesized polymers have been characterized by Fourier transform infrared spectroscopy solid-state 13C- and 29Si-NMR, thermogravimetric analysis, differential scanning calorimetry methods, and elemental analysis. In this report, the synthesis characterization, and swelling properties of crosslinked poly(orthosilicate)s for environmental removal and recovery of organic solvents are presented. The effect of the length of the aliphatic diol monomers on the properties of the synthesized polymers was also examined. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013