Poly(vinyl　ethylene　carbonate)　(PVEC)　electrolyte　is　one　of　the　preferable　choices　for　solid-state　lithium　metal　batteries　(SSLMBs).　However,　the　poor　anti-oxidation　ability　still　hinders　its　practical　application　for　high-energy　SSLMBs　with　high-voltage　cathodes.　Herein,　the　strategy　of　molecular　structure　adjustment　is　proposed　for　improving　the　properties　of　PVEC,　which　exhibits　the　widened　electrochemical　stability　window　(4.8　V　vs.　Li+/Li)　and　high　ionic　conductivity　(1.1　x　10(-3)　S　cm(-1)　at　25　degrees　C).　The　compatibilities　of　cathode/electrolyte　and　anode/electrolyte　interfaces　are　also　enhanced　respectively　by　eliminating　the　weak　bonding　of　polymer　mo-lecular　structure　and　forming　LixSn　alloy　during　the　ring-opening　polymerization.　The　solid-state　batteries　with　LiCoO2　cathode　exhibit　the　high　capacity　when　charged　to　4.5　V　at　25　degrees　C.　Therefore,　this　work　not　only　dem-onstrates　the　effective　method　to　enhance　the　interfacial　compatibility　between　electrolyte　and　electrode,　but　also　affords　an　emerging　design　strategy　for　polymer　electrolyte　by　breaking　the　unstable　weak　bonding　for　the　application　requirements　of　SSLMBs.