Solid　polymer　electrolytes(SPEs)are　urgently　required　to　achieve　practical　solid-state　lithium　metal　bat-teries(LMBs)and　lithium-ion　batteries(LIBs).Herein,we　proposed　a　mechanism　for　modulating　interfa-cial　conduction　and　anode　interfaces　in　high-concentration　SPEs　by　LiDFBOP.Optimized　electrolyte　exhibits　superior　ionic　conductivity　and　remarkable　interface　compatibility　with　salt-rich　clusters:(1)polymer-plastic　crystal　electrolyte(P-PCE,TPU-SN　matrix)dissociates　ion　pairs　to　facilitate　Li+transport　in　the　electrolyte　and　regulates　Li+diffusion　in　the　SEI.The　crosslinking　structure　of　the　matrix　compen-sates　for　the　loss　of　mechanical　strength　at　high-salt　concentrations;(2)dual-anion　TFSI-n-DFBOP-m　in　the　Li+solvation　sheath　facilitates　facile　Li+desolvation　and　formation　of　salt-rich　clusters　and　is　con-ducive　to　the　formation　of　Li　conductive　segments　of　TPU-SN　matrix;(3)theoretical　calculations　indicate　that　the　decomposition　products　of　LiDFBOP　form　SEI　with　lower　binding　energy　with　LiF　in　the　SN　sys-tem,thereby　enhancing　the　interfacial　electrochemical　redox　kinetics　of　SPE　and　creating　a　solid　interface　SEI　layer　rich　in　LiF.As　a　result,the　optimized　electrolyte　exhibits　an　excellent　ionic　conductivity　of　9.31　×　10-4　S　cm-1　at　30　℃　and　a　broadened　electrochemical　stability　up　to　4.73　V.The　designed　elec-trolyte　effectively　prevents　the　formation　of　Li　dendrites　in　Li　symmetric　cells　for　over　6500　h　at　0.1　mA　cm-2.The　specific　Li-Si　alloy-solid　state　half-cell　capacity　shows　711.6　mAh　g-1　after　60　cycles　at　0.3　A　g-1.Excellent　rate　performance　and　cycling　stability　are　achieved　for　these　solid-state　batteries　with　Li-Si　alloy　anodes　and　NCM　811　cathodes.NCM　811||Prelithiated　silicon-based　anode　solid-state　cell　delivers　a　discharge　capacity　of　195.55　mAh　g-1　and　a　capacity　retention　of　97.8％after　120　cycles.NCM　811||Li　solid-state　cell　also　delivers　capacity　retention　of　84.2％after　450　cycles.