The silanol condensation of hydrolyzed gamma-methacryloxypropyltrimethoxysilane (gamma-MPS) in the presence of a typical film-forming polymer, poly(vinyl acetate), PVAc, has been studied. The model sizing system, consisting of the hydrolyzates of gamma-MPS and PVAc obtained from the alcoholic aqueous solution, is studied using Fourier transform infrared spectroscopy (FT-IR) and size exclusion chromatography (SEC). In the initial stage of silanol condensation of the hydrolyzates of the model sizing system, it has been found that the condensation reaction is accelerated compared with the system that contains no film-former. It has also been found that the structure of gamma-MPS oligomer is relatively ordered and less-active for further silanol condensation. The least-square curve-fitting procedure for FT-IR spectra indicates five carbonyl stretching bands, reflecting the hydrogen bonded and the free carbonyl groups of the silane coupling agent and the film-forming polymer.