The kinetics of cationic polymerization of epoxy resin has been studied. Due to multiple reaction exotherms and irregular baselines involved in this system, the ASTM E 698 method was chosen to determine the kinetic parameters of this epoxy/BF3-MEA system. The DER 332/BF3-MEA system follows the first order active chain end (ACE) reaction mechanism. The adding of the hydroxyl group into the system is prone to decrease the activation energy and shifts the curing into the activated monomer (AM) mechanism due to the stronger nucleophilicity of the hydroxyl group than the epoxide group. On the other hand, the DER 331/BF3-MEA system possesses lower activation energy because the DER 331 contains more hydroxyl groups-alpha-glycol and secondary alcohol. The former is the major contributor in lowering the activation energy. The hydroxyl group also can act as a chain transfer agent by retarding the propagation process, thus the reaction rate of the DER 332/BF3-MEA system is higher than the DER 331/BF3-MEA system. The DER 332/BF3-MEA system shows good correlation between the experimental data (FT-IR, DSC, and GPC) and the simulation curve based on ASTM E 698 before gelation, while a larger deviation is observed in the DER 331/BF3-MEA system. After gelation, the hydroxyl group also acts as an active site to react with residual epoxy monomers and obtain a more condense matrix.