The overall kinetics of the thermal degradation of polyvinylcyclohexane (PVCH) were studied on a polymer produced from vinylcyclohexane by polymerization over system TiCl 4+Al (iso-C 4H 9) 3 as catalyst. Cyclohexane, cyclohexene, vinylcyclohexane, C 1C 4 hydrocarbons, hydrogen, and also traces of dicyclohexyl were identified as volatile decomposition products. The PVCH degradation is suggested to have a radical chain mechanism characterized by a dissociation of the cyclohexyl radical during initiation and a secondary ring opening with the liberation of lower hydrocarbons during the chain process.