AbstractRadical polymerizations of some cycloalkyl methacrylates bearing bridged‐ and fused‐ring structures, i.e., bornyl methacrylate (BoMA), isobornyl methacrylate (IBoMA), 2‐decahydronaphthyl methacrylate (DNMA), and 3‐tetracyclo [4.4.02,5.17,10] dodecyl methacrylate (TCDMA), were carried out. The radical polymerization reactivities of these monomers depended on the structure of the cycloalkyl ester groups in the following order: TCDMA>BoMA>DNMA>CHMA>IBoMA>MMA, where CHMA and MMA are cyclohexyl and methyl methacrylates, respectively. The propagation and termination rate constants of these monomers were evaluated from the polymer radical concentration determined by electron spin resonance spectroscopy. The solubilities and microstructures of the resulting polymers were examined. Thermal properties, i.e., glass transition temperatures and decomposition behaviors, of the polymers were also investigated and related to the structures of the polymer side chain. © 1993 John Wiley&S