Cobalt sulfide coupled with carbon materials attracts tremendous interest as a promising anode for Li-ion storage. In this paper, hollow Co3S4/C nanoparticles (NPs) with a uniform size of 30 nm homogeneously anchored on nitrogen-doped carbon nanofibers (denoted as Co3S4/CNF) are prepared by electrospinning method, followed by carbonization and sulfuration process. The free-standing Co3S4/CNF composites are straightly acted as binder- and current collector-free anode for lithium-ion battery, which demonstrate a high reversible capacity of 742 mAh·g−1 at 200 mA·g−1 after 200 cycles and 436 mAh·g−1 at 1 A·g−1 after 500 cycles, respectively. Such superior lithium storage performance of the Co3S4/CNF composites can be ascribed to the synergetic effect of the composites structure, which can effectively facilitate the electron and lithium ion diffusion, restrain the volumetric variation and keep the structure intact.