Given their competitive prospects for energy storage, lithium-ion batteries (LIBs) have attracted ever-intensive research interest. However, the large volume changes during cycling and structural pulverization significantly hinder the cycling stability and high capacity for lithium-alloy electrodes. Herein, novel one-dimensional (1D) hollow core-shell SnO2/C fibers were synthesized by facile coaxial electrospinning. The as-prepared fibers that possess sufficient hollow voids and nanosized SnO2 particles on the inner shell are able to serve as an anode in LIBs. The results suggest a reversible capacity of 1002 mAh g(-1) (for the initial cycle at 100 mA g(-1)), excellent rate capability, and a highly stable cycling performance with a discharge capacity of 833 mAh g(-1) after 500 cycles at 600 mA g(-1). The superior electrochemical performance is attributed to the unique hollow core-shell structure, which offers sufficient voids for alleviating the volume changes of SnO2 nanoparticles during lithiation/delithiation processes. The promising strategies and associated opportunities here demonstrate great potential in the fabrication of advanced anode materials for long-life LIBs.