Carbon nanofibers were prepared through electrospinning a blend solution of polyacrylonitrile and polypyrrole, followed by carbonization at 700°C. Structural features of electrospun polyacrylonitrile/polypyrrole bicomponent nanofibers and their corresponding carbon nanofibers were characterized using scanning electron microscopy, differential scanning calorimeter, thermo-gravimetric analysis, wide-angle X-ray diffraction, and Raman spectroscopy. It was found that intermolecular interactions are formed between two different polymers, which influence the thermal properties of electrospun bicomponent nanofibers. In addition, with the increase of polypyrrole concentration, the resultant carbon nanofibers exhibit increasing disordered structure. These carbon nanofibers were used as anodes for rechargeable lithium-ion batteries without adding any polymer binder or conductive material and they display high reversible capacity, improved cycle performance, relatively good rate capability, and clear fibrous morphology even after 50 charge/discharge cycles. The improved electrochemical performance of these carbon nanofibers can be attributed to their unusual surface properties and unique structural features, which amplify both surface area and extensive intermingling between electrode and electrolyte phases over small length scales, thereby leading to fast kinetics and short pathways for both Li ions and electrons.