We present the synthesis of nonsymmetric alpha-omega-functionalized polyisobutylenes (PIBs) bearing different functional moieties on their chain ends. Thus, on one chain end either, a short tri-ethylene oxide chain (TEO) or a phosphine oxide ligand is attached, whereas the other chain end is substituted by hydrogen bonding moieties (thymine/2,6-diaminotriazine). The nonsymmetric PIBs were synthesized via living cationic polymerization using methyl-styrene epoxide as initiator, followed by quenching reaction with 3-bromopropylbenzene. Subsequent bromide/azide exchange and the use of the azide/alkyne click reaction allowed the synthesis of (a) (alpha)-TEO-(omega)-thymine-telechelic PIB (7a), (b) (alpha)-triethyleneoxide-(omega)-triazine telechelic PIB (7b), and (c) (alpha)-phosphinoxide-(omega)-thymine-telechelic PIB (13) with molecular weights M(n) similar to 4000 g mol(-1) and low polydispersities (M(w)/M(n) = 1.3). The chemical identity of the final structures was proven by extensive (1)H NMR investigations and matrix-assisted laser desorption/ionization-mass spectroscopy (MALDI). The presented method for the first time offers a simple and highly versatile approach toward supramolecular nonsymmetric alpha-omega-functionalized PIB. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2931-2940, 2011