Polymer　electrolyte-based　solid-state　lithium　batteries　(SSLBs)　with　lithium-rich　layered　oxide　(LLO)　cathode　materials　can　provide　high　energy　density　and　safety.　However,　the　development　of　these　batteries　is　hindered　by　the　poor　anti-oxidation　ability　of　polymer　electrolytes.　Herein,　a　propanesultone-based　polymer　electrolyte　(PPS-PE)　is　designed,　and　a　wide　electrochemical　stability　window　(&　SIM;5.0　V　vs.　Li+/Li)　and　high　ion　transference　number　(&　SIM;0.78)　at　25　&　DEG;C　can　be　achieved.　The　strong　anti-oxidation　ability　of　PPS-PE　is　contributed　by　the　design　of　the　chain-like　molecular　structure,　and　the　hydrogen　bond　interactions　are　beneficial　for　inhibiting　the　anion　movement　of　Li　salt.　The　PPS-PE-based　SSLBs　with　LLO　cathode　materials　show　characteristic　charge/discharge　profiles　with　a　high　initial　discharge　capacity　of　&　SIM;270　mA　h　g-1　and　good　cycling　stability　at　25　&　DEG;C.　Therefore,　this　work　not　only　reports　a　novel　polymer　electrolyte　to　couple　with　high-voltage　cathodes　but　also　promotes　the　application　of　LLO　cathode　materials　in　high-energy　SSLBs.　A　propanesultone-based　polymer　electrolyte　with　high　ion　transference　number　of　&　SIM;0.78　and　wide　electrochemical　stability　window　of　&　SIM;5.0　V　has　been　designed　for　solid-state　lithium　batteries　with　lithium-rich　layered　oxide　cathode　materials.