An investigation was carried out on the effect of electrophilicity of amine molecule on the epoxy/amine reaction kinetics. Model systems, containing amines with different electron-donating and/or -withdrawing characteristics, were prepared, reacted, and investigated by high-performance liquid chromatography (HPLC). Reaction rate constants and activation energies were determined for all systems based upon a kinetic model of epoxy/amine reactions. It was established that an electron-donating group on the amine molecule enhanced the reaction rate and lowered the activation energy. It was also found that the reactivity ratio of primary amine/epoxy and secondary amine/epoxy reactions was dependent on the amine structure, but independent on temperature.