The polymerization of 4-vinyl-1-cyclohexene diepoxide (4-VCHD) by rhenium carbonyl, Re(CO)5X (X = Br, Cl) and dirhenium decacarbonyls Re 2 (CO) 10 has been carried out photochemically at 25 o C, and thermally at 25 and 75 o C witout cocatalysts. The effects of initiator structure, concentrations, and reaction temperature and time on the polymerization rate is reported here.