Novel Sb2S3@multiwalledcarbonnanotubes(MWCNTs) (SM) composites were synthesized via a facile and green method which included an in-situ growth of Sb2S3 nanoparticles on the surface of MWCNTs through precipitation and subsequent thermal treatment. The morphologies and structures of SM composites were tested by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and nitrogen adsorption and desorption isotherms. Finally, their application as anode materials for sodium-ion batteries (SIBs) was investigated through corresponding electrochemical measurements such as galvanostatic charge/discharge tests, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the SM composites display higher capacity, better cycling stability and superior rate performance than pure Sb2S3, and a capacity of 412.3mAhg−1 after 50 cycles at 50mAg−1 is obtained for SM composites with 30wt.% MWCNTs loading. The enhanced performance is ascribed to an increase in the specific surface area, an improvement in the charge transfer and effective buffering of the volume change offered by the porous conductive network structure of the composite with the introduction of MWCNTs.