Lithium　fluoride　(LiF)-rich　solid　electrolyte　interface　(SEI)　is　critical　for　enabling　the　stable　operation　of　polymer-based　all-solid-state　lithium-metal　batteries　(ASSLMBs).　Precisely　controlling　the　C　&　horbar;F　dissociation　chemistry　in　fluorine-containing　lithium　salts　to　construct　a　LiF-rich　SEI　is　a　logically　viable　but　still　challenging　approach.　Current　strategies　for　constructing　LiF-rich　SEI　primarily　focus　on　designing　non-metal　polar　groups　and　related　structures.　In　contrast,　approaches　leveraging　metal-based　electron　donors　to　facilitate　charge　transfer　for　C　&　horbar;F　bond　cleavage　and　LiF　formation　remain　largely　unexplored.　Herein,　a　dual-enhanced　charge　transfer　mechanism　through　prelithiation　strategy　is　proposed　in　solid　polymer　electrolyte　(SPE)　for　C　&　horbar;F　bond　cleavage.　The　charge　transfer　occurs　between　LiTFSI　and　the　introduced　metal　sites　and　further　enhanced　by　lithiation　design,　thereby　achieving　a　robust　LiF-rich　SEI.　The　achieving　SPEs　enable　an　excellent　cyclability　of　Li|Li　cell　over　3800　h　at　0.3　mA　cm-2.　Li||LiFePO4　ASSLMBs　demonstrate　a　high　Coulombic　efficiency　of　approximate　to　100%　and　a　stability　of　1200　cycles　with　capacity　retention　of　80%　at　2C.　The　corresponding　pouch　cell　delivers　a　high　average　areal　capacity　of　2.41　mAh　cm-2　over　1600　h.　This　work　offers　a　novel　approach　for　constructing　LiF-rich　SEI　toward　durable　ASSLMBs.