Simultaneously achieving a high conductivity and a good volume-change accommodation for sulfur cathode in lithium‑sulfur batteries is highly required. Herein, we present a unique porous sulfur composite consisting of a porous sulfur particle coating with conductive hydrogel polypyrrole, which is prepared through a templated method. The pores inside the sulfur particles offer a good buffering space for the volume expansion of sulfur upon lithiation; while the external polypyrrole coating improves the conductivity and suppress the transfer of polysulfides. The porous sulfur@polypyrrole composite exhibits a capacity of about 900 mAh g−1 after cycling for 100 times at 0.12C, along with a good Coulombic efficiency around 99.9%, which is much better than the polypyrrole-coated non-porous sulfur particles and pure sulfur particles. When cycled for 500 times, the capacity fading rate is as low as 0.09% per cycle. After three rounds of rate-performance measurements, the capacity retention of the sulfur@polypyrrole at different rates remain above 97%. The density functional theory calculations and electrochemical impedance spectra demonstrate a polysulfide-adsorptive and a stable electric transportation surface of the sulfur@polypyrrole composite, respectively.