Living cationic polymerization of 2-adamantyl vinyl ether (2-vinyloxytricyclo[3.3.1.1](3,7)decane; 2-AdVE) was achieved with the CH3CH(OiBu)OCOCH3/ethylaluminum sesquichloride/ethyl acetate [CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5/CH3COOEt] initiating system in toluene at 0 degrees C. The number-average molecular weights (M-n's) of the obtained poly(2-AdVE)s increased in direct proportion to monomer conversion and produced the polymers with narrow molecular weight distributions (MWDs) (M-w/M-n = similar to 1.1). When a second monomer feed was added to the almost polymerized reaction mixture, the added monomer was completely consumed and the Mn's of the polymers showed a direct increase against conversion of the added monomer. Block and statistical copolymerization of 2-AdVE with n-butyl vinyl ether (CH2=CH-O-CH2 CH2CH2CH3; NBVE) were possible via living process based on the same initiating system to give the corresponding copolymers with narrow MWDs. Grass transition temperature (T,) and thermal decomposition temperature (T-d) of the poly(2-AdVE) (e.g., M-n = 22,000, M-w/M-n = 1.17) were 178 and 323 degrees C, respectively. (C) 2008 Wiley Periodicals, Inc.