The effect of pores in hollow carbon nanofibers (HCNFs) on their electrochemical performance is investigated because the carbon shell itself acts as a reservoir for accommodating Li-ions through intercalation and simultaneously becomes a transport medium through which Li-ions migrate into the core materials in HCNFs. Porous HCNFs (pHCNFs) are prepared by the coaxial electrospinning of a sacrificial core solution and an emulsified shell solution containing sacrificial islands for pore generation. After a thermal treatment, a systematic study is carried out to relate the resulting pore size in pHCNFs to the sacrificial islands in the emulsified shell. As the pores are introduced in pHCNFs, their initial capacity and reversible capacity rate are proved to increase significantly to 1003 mAhg(-1) and 61.8%, respectively, compared to those (653 mAhg(-1) and 53.9%) of nonporous HCNFs. The increased pore size and expanded graphene layers are believed to facilitate lithium insertion/extraction behavior.