A novel multi-step method that combines solvothermal, sulfidation and polymerization process was utilized to synthesize Antimony Sulfide/Meso@Microporous Carbon nanofibers@polypyrrole (Sb2S3/MMCN@ppy) composite. As the host, the MMCN is full of microporous and mesoporous naturally, which can prevent the aggregation during the sulfidation process and accelerate the transfer of electron inside the whole composite. Meanwhile, the effective coverage of ppy layer can accommodate the volume changes during cycling and fast the electron transfer on the surface of the composite. Combining those merits, the dual physical barrier composed of MMCN and conductive ppy layer guarantees the ultrastable structure for superior electrochemical performance. When used as an anode for lithium-ion batteries, Sb2S3/MMCN@ppy composite demonstrates the stable electrochemical performance with an enhanced lithium-storage capability. Impressively, even at the high current density of 1000 mA g−1, a specific reversible capacity about 556 mA h g−1 can be delivered after 300 long cycles. In addition, Sb2S3/MMCN@ppy composite also displays the outstanding stability sodium-storage property in sodium-ion batteries (269 mAh g−1 at 1000 mA g−1 after 300 long cycles). The results show that this product may be considered as a promising anode material for advanced LIBs and SIBs.