AbstractThe kinetics of the bulk thermal polymerization of phenyl glycidyl ether induced by trimethoxyboroxine were investigated. Infrared absorption spectroscopy and gel permeation chromatography were used to follow the course of polymerization, while proton and boron‐11 NMR spectroscopy were used to support the kinetic model developed. The postulated mechanism involves a fast‐initiated, nonstationary cationic polymerization with five elementary steps, including spontaneous and monomer transfer as well as a termination reaction. The trimethoxyboroxine was found to be incorporated into the structure of the cured polymer. The polymerization was followed at several temperatures and with several ratios of initial concentrations of trimethoxyboroxine to phenyl glycidyl et