Silicon is regarded as one of the most promising candidates for lithium-ion battery anodes owing to its large theoretical energy density (about 4200 mAh g−1) and low working potential (vs. Li/Li+). However, its practical application is limited by structure degradation and a comparatively poor capacity retention caused by large volume changes during cycling. In this study, we have prepared a novel nanofiber form of silicon/carbon with hollow core–shell structured silicon@carbon (Si@C) nanoparticles embedded in carbon nanofibers. Voids between the silicon nanoparticle (SiNP) core and carbon shell help to accommodate the volume expansion associated with the lithiation/delithiation process in a working electrode and allow formation of a stable solid electrolyte interphase (SEI) film. The obtained electrodes exhibited good cycle performance with a high reversible capacity of 1020.7 mAh g−1 after 100 cycles at a current density of 0.2 A g-1, and also delivered excellent cycling performance at a high current density of 3.2 A g-1. The design of this new structure provides a potential method for developing other functional composite anode materials with high reversible capacities and long-term cycle stabilities.