Provided is an all-solid-state lithium rechargeable cell, comprising: a) a cathode, wherein the cathode comprises: a1) a composite of VS4 and graphene; and a2) a solid catholyte; and b) a lithium-based anode. In particular, the all-solid-state lithium rechargeable cell of the present disclosure may exhibit high initial discharge capacities, high initial Coulombic efficiencies, good reversible capacities, excellent cycling stabilities, high energy densities as well as outstanding safeties.