‘Corn-on-the-cob’ structured ZnS nanoparticles anchored on porous carbon nanofibers (ZnS/PCNFs) were rationally designed and prepared using preoxidized PVA/PTFE nanofibers as porous matrix precursors through subsequent solvothermal and carbonization. The obtained ZnS/PCNFs composite as anode material for lithium ion batteries exhibit a promising cycling performance with high reversible capacity of 718 mAh g−1 at 0.2 A g−1 after 150 cycles and excellent rate capability with discharge capacity of 438 mAh g−1 at 2 A g−1. The prominent battery performance of ZnS/PCNFs electrode might be ascribed to the distinct hybrid structure, where the uniformly arranged nanosized ZnS ‘corns’ endowed the hybrid with excellent lithium capacitive performance, and the rationally designed PCNFs ‘cob’ with large specific surface area not only improved the conductivity but also enhanced the diffusion of electrolyte and ion movement within the hybrid.