Cationic polymerization of isobutyl vinyl ether (IBVE) was examined using a variety of metal oxides in conjunction with IBVE-HCl adduct as a cationogen in toluene at 0 degrees C. Iron oxides (alpha-Fe2O3, gamma-Fe2O3, and Fe3O4) induced living polymerization in the presence of an added base, ethyl acetate or 1,4-dioxane, to give polymers with very narrow molecular weight distributions (MWDs). Conversely, with other metal oxides such as Ga2O3, In2O3, ZnO, Co3O4, and Bi2O3, polymers with bimodal MWDs, including long-lived species along with uncontrolled higher molecular weight portions, were produced in the presence of an added base. A small amount of nBu(4)NCl or 2,6-di-tert-butylpyridine (DTBP) suppressed the uncontrolled portion to induce controlled reactions with Ga2O3, In2O3, and ZnO. The roles of these reagents are discussed in terms of the nature of the active sites of the catalyst surface and the polymerization mechanisms. In addition, the reusability of the catalyst, the effect of stirring before and during polymerization, and the estimation of the number of active sites are also described. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48:916-926, 2010