To solve large volume change and low conductivity of Bi 2 S 3 -based anodes, a coordination regulation strategy is proposed to prepare Bi 2 S 3 nanoparticles dispersed in carbon fiber (Bi 2 S 3 @CNF) composites. It has been discovered that introducing trimesic acid as a ligand can significantly improve the loading and dispersion of Bi 3+ in polyacrylonitrile fibers. The results exhibit that Bi 2 S 3 nanoparticles of 200−300 nm are uniformly anchored on the superficial surface layer of CNFs, and Bi 2 S 3 nanoparticles of about 20 nm are evenly dispersed in the interior of CNFs. Assessed as sodium-ion batteries' anode material, the discharge capacity of the Bi 2 S 3 @CNF anode in the second cycle is 669.3 mAh g −1 at 0.1 A g −1 and still retains 620.2 mAh g −1 after 100 cycles, with the capacity retention rate of 92.7%. Even at 0.5 A g −1 , the specific capacity of the second cycle is 432.99 mAh g −1 , which still keeps 400.9 mAh g −1 after 800 cycles, with a retention rate of 92.5%. The excellent cycle stability is mainly attributed to the uniform distribution of small Bi 2 S 3 nanoparticles in CNFs providing abundant active sites, preventing side reactions, relieving volume expansion, improving the electrical conductivity, and accelerating the electrochemical reaction kinetics.