The synthesis of a series of difunctional epoxides bearing two epoxycyclohexyl groups linked together by an alkylene ether group has been carried out. Subsequently, the reactivities of these novel monomers was investigated and compared to the reactivity of the cycloaliphatic epoxide, 3,4-epoxycyclohexylmethyl 3’,4’-epoxycyclohexane carboxylate (I) in photoinitiated cationic polymerization. It was observed that alkylene oxide linking the two epoxycyclohexyl groups was short and the monomers are more reactive than I. The effects of the photoinitiator structure and the experimental conditions of the cationic photopolymerization on the rates was also studied using real-time infrared spectroscopy.