Polyacrylonitrile (PAN)/polyphenylsilane (PPS)-based composite carbon nanofibers (CCNFs) are prepared by one-step electrospinning and subsequent thermal treatment to produce organic-inorganic hybrid CCNFs. We investigate the electrochemical behavior and structural properties of these CCNF materials as a function the PAN/PPS ratio. The CCNFs show large specific surface area, high electrical conductivity and high thermal stability. In addition, the electrochemical performance of the organic-inorganic hybrid CCNF electrode is improved by the special porous structure and the silicon oxycarbide (Si-O-C)-related structure. (C) 2011 Elsevier Ltd. All rights reserved.