This work presents a facile synthesis approach for core-shell structured Li2S nanoparticles with Li2S as the core and Li3PS4 as the shell. This material functions as lithium superionic sulfide (LSS) cathode for long-lasting, energy-efficient lithium-sulfur (Li-S) batteries. The LSS has an ionic conductivity of 10(-7) S cm(-1) at 25 °C, which is 6 orders of magnitude higher than that of bulk Li2S (∼10(-13) S cm(-1)). The high lithium-ion conductivity of LSS imparts an excellent cycling performance to all-solid Li-S batteries, which also promises safe cycling of high-energy batteries with metallic lithium anodes.