Abstracts A conductive polyaniline-wrapping hollow sulfur composite used as a cathode material for lithium/sulfur batteries was successfully fabricated by a facile and controllable chemical reaction with MCM-41 template. The polyaniline-wrapping hollow sulfur composite had a good reversible capacity of 506.3 mAh g−1 at the 150th cycle, reflecting the low loss of sulfur and polysulfide encapsulated by polyaniline during the charge and discharge cycles. The results of SEM and EIS show that the polyaniline-wrapping hollow sulfur composite presented many good electron-conducting paths for the rechargeability of lithium/sulfur battery. XRD and TG-DSC results revealed the formation of fine sulfur particles encapsulated by polyaniline and sulfur distributed on the polyaniline surface because of low sulfur melting temperature, which was the key reason for the activation.