The di-functional epoxy resins, i.e., diglycidylether of bisphenol A(DGEBA) and diglycidylethere of bisphenol F(DGEBF) were initiated by cationic catalyst, i.e., benzylquinoxalinium hexafluoroantimonate(BQH) using electron-beam(EB) technique. And the effect of structure of DGEBA and DGEBF on thermal stabilities and cure behaviors was investigated. According to the experimental results, the decomposed activation energy based on Horowitz-Metzger method was higher in the case of DGEBA, but intergral procedural decomposition temperature(IPDT) of DGEBA was lower than DGEBF. This could be interpreted in terms of high crosslink density resulted from hydroxyl bond of DGEBF backbone. It was confirmed in increasing the hydroxyl band at $7000;cm^{-1}$ and $5235;cm^{-1}$ using near-infrared spectroscopy(NIRS).