A Li6PS5Cl solid electrolyte was successfully prepared by dissolution-reprecipitation process via ethanol solution. An ionic conductivity of the Li6PS5Cl solid electrolyte from the homogeneous ethanol solution was 1.4 × 10−5 S cm−1 at room temperature. LiCoO2 particles were coated with the Li6PS5Cl electrolyte via ethanol solution to form favorable electrode-electrolyte interface with a large contact areas. An all-solid-state cell using the electrolyte-coated LiCoO2 operated as a rechargeable battery and showed the initial discharge capacity of 45 mAh g−1 at 25 °C.