A favorable Si (core)-hollow carbon nanofiber (sheath) nanocomposite, was synthesized by a coaxial electrospinning technique. As a potential anode material for LIBs, this composite displays a high reversible capacity of 1300 mA h g(-1) even after 80 cycles at 0.5 C. It also exhibits a reversible discharge capacity as high as 700 mA h g(-1) when cycled at 3 C. This makes the Si-C composite a promising candidate for use as an anode material in lithium ion batteries. Beyond that, coaxial electrospinning has proved itself as a powerful technique to prepare nanomaterials with hollow core-shell architectures.