We designed solid-state hybrid electrolytes with single-ion conducting properties by co-assembling binary core-shell polymer nanoparticles. By controlling the nanoparticle size and number, we created superlattices that optimized the Li+ concentration and transport. The electrolytes exhibited a remarkable ionic conductivity (10-4 S cm-1), lithium transference number (0.94), electrochemical stability (up to 6 V), and modulus (0.12 GPa) at 25 °C. The mechanical strength of these electrolytes depended minimally on temperature at 25-150 °C because of the robustness of the cores. When implemented in Li-S batteries with no liquids, they demonstrated an initial discharge capacity of 1090 mA h g-1 at 0.05C, a cycle life of over 200 cycles, and a rate capability with a discharge capacity of 627 mA h g-1 at 3C.