Living cationic polymerization of a vinyl ether with a naphthyl group [2-(2-naphthoxy)ethyl vinyl ether, beta NpOVE] was achieved using base-assisting initiating systems with a Lewis acid. The Et1.5AlCl1.5/1,4-dioxane or ethyl acetate system induced the living cationic polymerization of beta NpOVE in toluene at 0 degrees C. The living nature of this reaction was confirmed by a monomer addition experiment, followed by 1H NMR and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analyses. In contrast, the polymerization of aNpOVE was not fully controlled; under similar conditions, it produced polymers with broad molecular weight distributions. The 1H NMR and MALDI-TOF-MS spectra of the resultant poly(aNpOVE) revealed that the products had undesirable structures derived from FriedelCrafts alkylation. The higher reactivity of aNpOVE in electrophilic substitution reactions, such as the FriedelCrafts reaction, was attributable to the greater electron density of the naphthyl ring, which was calculated based on frontier orbital theory. The naphthyl groups significantly affected the properties of the resultant polymer. For example, the glass transition temperatures (Tg) of poly(NpOVE)s are higher by approximately 40 degrees C than that of poly(2-phenoxyethyl vinyl ether). (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012