This article presents the first detailed account of the discovery that substituted epoxides can initiate the carbocationic polymerization of isobutylene. ␣-Methylstyrene epoxide (MSE), 2,4,4-trimethyl-pentyl-epoxide-1,2 (TMPO-1), 2,4,4-trimethylpentyl-epoxide-2,3 (TMPO-2), and hexaepoxi squalene (HES) initiated isobutylene polymerization in conjunction with TiCl 4 . MSE, TMPO-2, and HES initiated living polymerizations. A competitive reaction mechanism is proposed for the initiation and propagation. According to the proposed mechanism, initiator efficiency is defined by the competition between the S N 1 and S N 2 reaction paths. A controlled initiation with external epoxides such as MSE should yield a primary hydroxyl head group and a tert-chloride end-group. The presence of tert-chloride end-groups was verified by NMR spectroscopy, whereas the presence of primary hydroxyl groups was implied by model experiments. Multiple initiation by HES was verified by diphenyl ethylene end-capping and NMR analysis; the resulting star polymer had an average of 5.2 arms per molecule. A detailed investigation of the reaction mechanism and the characterization of the polymers are in progress.