The ZnO/SnO2 heterogeneous nanofibers (HNFs) have been prepared via an electrospinning method followed by calcination at 500°C in air. XRD, BET, SEM, TEM and electrochemical measurements were performed to characterize the new material, including structure, morphology and electrochemical properties. The spacing between adjacent SnO2 nanorods on mesoporous ZnO nanofibers is about twice the diameter of each SnO2 nanorod. The SnO2/ZnO11 (molar ratio of Sn: Zn=1:1) HNFs based electrodes exhibit excellent cycle performance and rate performance, which is attributed to the heterogeneous and mesoporous structure as well as the ultrafine ZnO NPs embedded in the HNFs matrix. Outstanding electrochemical performance as anode material for LIBs together with low cost, facile procedures and high reproducibility make the SnO2/ZnO HNFs have a prospect in the field of energy storage.