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.