Poly(silyl ester)s were synthesized by a new route via the condensation of di-tert-butyl ester of dicarboxylic acid with dichlorosilane by the elimination of tertbutyl chloride as a driving force. Three new poly(silyl ester)s with molecular weights typically ranging from 2000 to 5000 amu were produced by the condensation of di-teyt-butyl adipate with 1,5-dichloro-1,1,5,5-tetramethyl-3,3-diphenyl trisiloxane and di-tert-butyl fumarate with 1,5-dichloro-1,1,5,5-tetramethyl-3,3-diphenyl trisiloxane or 1,3-dichlorotetramethyl disiloxane. Each polymer was characterized with infrared H-1-NMR, and C-13-NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. This new approach showed several advantages. First, it did not require a catalyst or solvent. Second, the tert-butyl chloride byproduct was volatile and was easily eliminated. Third, there was no reaction between the growing poly(silyl ester)s and the condensation byproduct, tert-butyl chloride. Fourth, the monomers could be readily purified. Finally, the polymerization could be performed at relatively low temperatures and in a short time.