Decoration of polymers onto nanoparticles has drawn much scientific and technological interest due to the potential for directed assembly of large-scale nanoarchitectures. However, there have been no previous reports on such decoration of polymers derived from highly-ordered inorganic organic nanolayered features that have the potential to chemically bond to the nano-reinforcement. In this work, polymers derived from octadecyltrimethoxysilane (ODMS) were successfully decorated onto carbon nanofibers (CNFs) yielding unique hybrid shish-kebab structures. Interestingly, only under highly alkaline conditions were shish-kebab structures formed onto the CNFs. Chemical characterization of the polymeric shish-kebab structure was performed using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and nuclear magnetic resonance (NMR), indicating extended hydrocarbon chains with crosslinking of the siloxane groups. For the siloxane polymer with the distinctive shish-kebab forming structure, NMR results showed that there was an incomplete reaction of siloxane groups, which may have facilitated heterogeneous crystallization of the polymer onto the Ox-CNFs. Potential applications for these unique nanohybrid structures are discussed. (c) 2012 Elsevier Ltd. All rights reserved.