Ternary graphene/sulfur/polyaniline (graphene/S/PANI) composites have been successfully prepared via a facile two-step synthesis method. S nanoparticle is uniformly decorated on the graphene surface, and PANI nanowires cover the graphene/S surface. When used as cathode material for lithium-sulfur batteries, the specific ternary composite achieves excellent electrochemical performance with high capacity and improved cycling stability. The graphene/S/PANI sample delivers a specific capacity of up to 837mAhg−1 after a few cycles at 0.1C, which is considerably higher than that delivered by the graphene/S sample. In addition, the graphene/S/PANI sample and the graphene/S sample show improved cycling stability with improved Coulombic efficiency compared with pure S sample. This observation indicates the successful prevention of the polysulfide species diffusion owing to graphene introduction. Furthermore, the activation mechanism of graphene/S is studied through morphology change during cycling, which demonstrates that activation is ascribed to the gradual spread of S on the graphene surface during cycling.