In this article, we report the noncovalent linkage of terminal substituted oligo(dimethylsiloxanes) bearing cyclodextrins (CD) as host endgroups and adamantan or ferrocene, respectively, as guest endgroups. Structural characterization was performed by 1H NMR-, IR-, and mass spectroscopy. Electron microscopy studies show significant differences in the surface structure of the individual derivatives. In addition, the ferrocene-terminated di-and poly(dimethylsiloxanes) are distinguished by a red-ox activity and reversibility, which also makes the complexes between the ferrocene- and CD functionalized siloxanes switchable via electrochemical stimuli. The evidence for a successful complexation of the end groups, and thus the successful supramolecular formation of the siloxane strands, was even performed by shift of the protons in the 1H NMR spectra. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2472-2482