Polyvinyl chloride (PVC) powders are introduced as carbon sources to prepare Si–SnSb alloy based on carbothermal method. Then the as-prepared alloy was mixed with pyrolytic polyacrylonitrile (PAN) to synthesize a composite anode of Si–SnSb/ pyrolytic polyacrylonitrile (PAN) with the pyrolysis of PAN at 400°C and 600°C. The material exhibits a high-specific capacity and a good-cycling stability due to its multiphase characteristics. The Si–SnSb blended with PAN pyrolyzed at 600°C shows better electrochemical performance, its initial Coulombic efficiency is 62.6%, and the specific capacity is 658.4mAhg−1 after the 10th cycle. The pyrolytic PAN improves the performance of the Si–SnSb alloy by means of dispersing the alloy efficiently, and the pyrolytic PAN enhances the performance of the pure alloy simultaneously.