Solid　polymer　electrolytes　(SPEs)　applied　to　all-solid-state　lithium　metal　batteries　(ASSLMBs)　can　construct　energy　storage　devices　with　high　safety　and　high　energy　density.　However,　it　restricts　the　application　due　to　the　low　ionic　conductivity　and　slow　lithium　transport　of　SPEs　lead　the　inhomogeneous　deposition　of　Li.　Herein,　a　free-standing　SPEs　designed　by　introducing　polyether　block　amide　(Pebax)　and　polyethylene　glycol　(PEG)　as　additive　to　obtain　the　inspired　PP-SPE,　which　can　be　prepared　at　scale.　PEG　addition　helped　Pebax　connecting　to　form　a　network　structure.　Through　the　synergistic　effect　of　Li+　and　ether　oxygen　or　carbonyl　group　in　Pebax.　which　promoted　the　rapid　lithium　transport　and　exhibited　a　high　ionic　conductivity　of　4.27　x　10-4　S　cm-　1　(room　temperature)　and　a　relative　high　lithium　ion　transference　number　(0.44).　In　addition,　the　prepared　SPEs　had　good　mechanical　properties　(5.1　MPa).　The　highly　stable　interface　with　lithium　metal　was　maintained　for　more　than　600　h　at　a　current　density　of　0.1　mA　cm-　2,　and　no　dendrite　growth　observed.　The　capacity　of　the　Li//LFP　cell　was　108　mAh　g-　1　at　room　temperature　and　0.5C　with　96.5　%　capacity　retention　after　300　cycles.　Thus,　PPSPE　provides　a　new　strategy　for　the　safety　and　high　energy　density　of　commercialization　ASSLMBs.