Porous carbon nanofibers were prepared by the electrospinning of a bicomponent polymer solution, followed by thermal treatments under different atmospheres. The surface morphology, thermal properties, and crystalline features of these nanofibers were characterized using various analytic techniques, and it was found that they were formed with turbostratically disordered graphene sheets and had small pores and large surface areas. The unique structure of these porous carbon nanofibers resulted in good electrochemical performance such as high reversible capacity and good cycle stability when they were used as anodes for rechargeable lithium-ion batteries.