Sandwich-type porous carbon/sulfur/polyaniline (SPC–S–PANI) composite with active sulfur nanoparticles confined within porous carbon is prepared. As a cathode material for Li–S batteries, the SPC–S–PANI composite with over 60 wt% sulfur content delivers high reversible capacity up to 1335 mA h g⁻¹ for the first cycle and 834 mA h g⁻¹ maintained over 100 cycles at 0.1C with an high coulombic efficiency of 96.5%. The high performance is attributed to the rationally designed hierarchical structure, which resulted in increased electrical conductivity, and hampered the dissolution of lithium polysulfide and provided a large pore volume for sulfur impregnation. Based on these merits, this sandwich-type porous carbon/polyaniline sulfur cathode shows the great potential for application in high-performance lithium–sulfur batteries.