Polyacrylonitrile sulfide (PAN-S) was synthesized for use as a positive electrode of a lithium rechargeable battery. To assemble the lithium rechargeable battery with an all-solid-state cell configuration, we also prepared a quasi-solid-state electrolyte consisting of a room temperature ionic liquid (RTIL)-like equimolar complex of tetraethylene glycol dimethyl ether (tetraglyme, G4)-lithium bis(trifluoromethanesulfonyl)amide (Li-TFSA) and fumed silica nanoparticles. The lithium rechargeable battery with the PAN-S positive electrode, quasi-solid-state electrolyte and lithium negative electrode showed high capacity and good cycle performance. The 2nd and 50th discharge capacities were 450 and 390 mAh g(-1), respectively, with nearly 100% Coulombic efficiency without remarkable capacity fade during the operation. (C) 2013 Elsevier B.V. All rights reserved.