The aldol addition of dimethylsilyl enolates to aldehydes with alkali metal salt catalysts was examined. Several kinds of polyether derivatives were employed as solid solvents without a liquid one. In the presence of the polymer (Gr) obtained from poly(ethylene glycol) methyl ether methacrylate (PEGMA) or the crosslinked derivatives (GLs) from PEGMA, the aldol addition proceeded efficiently and yielded the product. The effective catalyst was lithium bromide for Gr and potassium bromide for GLs. The crosslinked polyether GLs were easily separated from the reaction mixture by simple filtration, which was preferable to simplifying the treatments of the reaction. The results demonstrated that the presence of polyether structures provided a favorable reaction environment and enabled the reaction under solvent-free conditions. (c) 2005 Wiley Periodicals, Inc.