This article reports the facile synthesis of novel terminally and centrally functionalized polyisobutylenes (PlBs) and the detailed characterization of the products by various mass spectrometry techniques. Specifically, H-PlB-CH2-C(OH)CH3-CH2-NHCH3 and [H-PIB-CH2-CH(OH)CH3-CH2](2)-NCH3 were synthesized by the quantitative epoxidation of H-PIB-CH2-(CH3)=CH2 and the subsequent conversion of the resulting epoxide with excess CH3NH2. Quaternization with CH3Cl of these mixtures of secondary and tertiary amines yielded exclusively H-PIB-CH2-C(OCH3)CH3-CH2-N(CH3)(2) from the secondary amine, whereas the tertiary (centrally functionalized) amine remained unchanged. Tandem mass spectrometry experiments provided unique insight into the precise connectivity of the functional end groups added to the PIB frame. (C) 2005 Wiley Periodicals, Inc.