A porous TiO2/BaTiO3 heterostructure composite has been developed as a polysulfide mediator for lithium-sulfur batteries. Superior electrochemical performance has been achieved, mainly attributed to the synergy of TiO2 and BaTiO3 with dual affinity to polysulfides from chemical and ferroelectric-induced polarization effects, and enhanced redox kinetics propelled by the TiO2/BaTiO3 heterojunctions.