The polymerization of 2-tert-butylcyclohexyl methacrylate (2BCHMA) was carried out in benzene at 60-degrees-C. The polymerization reactivity of 2BCHMA decreased due to the steric effect of the ester substituent compared to other alkyl methacrylates (RMA) including 4-tert-butylcyclohexyl methacrylate (4BCHMA). The evaluation of propagation and termination rate constants by electron spin resonance spectroscopy revealed that both the propagation and the termination were suppressed by the 2-tert-butyl substituent in the cyclohexyl moiety. The microstructure and thermal properties of poly(2BCHMA) were also examined and compared with those of poly(4BCHMA).