The living cationic polymerization of 6-tert-butoxy-2-vinylnaphthalene (tBOVN), a vinylnaphthalene derivative with an electron-donating group, was achieved with a TiCl4/SnCl4 combined initiating system in the presence of ethyl acetate as an added base at -30 degrees C. The absence of side reactions at low temperature was confirmed by H-1 NMR analysis of the resulting polymer. In contrast to this controlled reaction at -30 degrees C, reactions performed at higher temperature, such as 0 degrees C, frequently involved unwanted intramolecular or intermolecular Friedel-Crafts reactions of naphthalene rings due to the high electron density of these rings. The cationic polymerization of 6-acetoxy-2-vinylnaphthalene, a derivative with an acetoxy group, was also controlled under similar conditions, but chain transfer reactions were not completely suppressed during the polymerization of 2-vinylnaphthalene. The glass transition temperature (T-g) of the obtained poly(tBOVN) was 157 degrees C, a value higher by 94 degrees C than that of the corresponding styrene derivative. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4828-4834