Compositing　inorganic　ceramics　and　polymer　materials　to　form　all-solid-state　electrolytes　has　been　recognized　as　a　feasible　approach　for　the　development　of　all-solid-state　batteries.　However,　polymer-based　electrolytes　such　as　polyethylene　oxide　can　electrochemically　decompose　above　3.9　V　(vs.　Li+/Li),　which　results　in　undesirable　battery　performance.　Moreover,　dendrite　growth　can　occur　on　the　anode　side　and　further　lead　to　battery　short-circuit.　This　work　designs　and　successfully　fabricates　stable　electrode/electrolyte　interfaces　on　both　the　composite　cathode　and　anode　sides　after　employing　alucone　coating　layers　made　through　atomic　layer　deposition.　Due　to　the　protection　capability　of　such　coating　layers,　the　electrochemical　degradation　between　the　composite　solid-state　electrolytes　of　Li7La3Zr2O12/polyethylene　oxide/lithium　bis(trifluoromethane-sulfonyl)　imide　film　and　nickel-rich　high　voltage　cathode　(LiNi0.8Mn0.1Co0.1O2)　has　been　obviously　suppressed　through　the　significantly　improved　anti-　oxidation　capability　of　the　electrolyte.　Simultaneously,　the　alucone　coating　layer　can　function　as　the　protective　barrier　for　the　lithium　metal　anode,　remarkably　suppressing　the　growth　of　lithium　dendrites.　As　a　result,　the　obtained　all-solid-state　batteries　with　dual　electrode/electrolyte　interfaces　show　both　high　capacity　retention　and　long　cycle　life,　whereas　the　contrasting　battery　without　protection　coating　layers　shows　both　the　fast　capacity　decay　and　micro-shorting　behavior.　This　work　presents　an　effective　strategy　for　constructing　more　stable　electrode/electrolyte　interfaces　for　polymers-based　all-solid-state　batteries,　and　also　provides　a　design　rationale　for　materials　and　structure　development　in　the　field　of　energy　storage　and　conversion.