S/Bi2S3/C composites have been prepared based on melt strategy at 280 °C starting from metallic bismuth (mp 271.3 °C), excess sulfur powder and porous carbon with different ratio. In the as-prepared composites, the in-situ formed Bi2S3 in molten S environment can homogeneously dispersed in S and carbon. Combining the physical confinement of porous carbon and chemical interaction of the in-situ formed Bi2S3, the dissolution of polysulfides has been well inhibited. Thus, the obtained S/Bi2S3/C composite exhibits good electrochemical performance, which could deliver capacity of ∼825 mAh g−1 at 0.5 C over 400 cycles, with 91% capacity retention and high Coulombic efficiency.