This work reports on hollow carbon nanofibers (HCNFs) as anode materials for Li-ion batteries. Various HCNFs are synthesized using co-axial electrospinning of styrene-co-acrylonitrile (core) and poly(acrylonitrile) (shell) solutions and subsequent thermal treatments. The microstructures of HCNFs are examined using SEM, Raman spectroscopy, WAXD, and HR-TEM. The effect of the carbonization temperature on their turbostratic carbon structures and electrochemical properties is systematically investigated. As the carbonization temperature increases, both crystallite thickness and length significantly increases while the initial irreversible capacity decreases. These predictable microstructure and electrochemical performance of HCNFs provide important insight for the design of novel nanostructured anode materials such as Si or Sn encapsulated HCNFs.