Polyacrylonitrile-S/carbon composite with highly dispersed polyacrylonitrile-S in porous carbon was prepared by a feasible heat-treatment method. Excellent electrochemical performance of this composite was gained although the carbonization of polyacrylonitrile polymer chain was low. The retention capacity of polyacrylonitrile-S/carbon composite was up to 658.8 mAh g −1 after 50 cycles, delivering 95% of the charging capacity in the second cycle. Polyacrylonitrile-S/carbon exhibited excellent reversible lithium storage capability at high current rate, resulting in a value of 518.2 mAh/g at 0.65 mA cm −2 , prior to other polyacrylonitrile-S composite. The enhancement attributes to the composite structure with porous carbon as the host.