Considering　the　growing　pre-lithiation　demand　for　high-performance　Si-based　anodes　and　consequent　additional　costs　caused　by　the　strict　pre-lithiation　environment,　developing　effective　and　environmentally　stable　pre-lithiation　additives　is　a　challenging　research　hotspot.　Herein,　interfacial　engineered　multifunctional　Li13Si4@perfluoropolyether　(PFPE)/LiF　micro/nanoparticles　are　proposed　as　anode　pre-lithiation　additives,　successfully　constructed　with　the　hybrid　interface　on　the　surface　of　Li13Si4　through　PFPE-induced　nucleophilic　substitution.　The　synthesized　multifunctional　Li13Si4@PFPE/LiF　realizes　the　integration　of　active　Li　compensation,　long-term　chemical　structural　stability　in　air,　and　solid　electrolyte　interface　(SEI)　optimization.　In　particular,　the　Li13Si4@PFPE/LiF　with　a　high　pre-lithiation　capacity　(1102.4　mAh　g-1)　is　employed　in　the　pre-lithiation　Si-based　anode,　which　exhibits　a　superior　initial　Coulombic　efficiency　of　102.6%.　Additionally,　in　situ　X-ray　diffraction/Raman,　density　functional　theory　calculation,　and　finite　element　analysis　jointly　illustrate　that　PFPE-predominant　hybrid　interface　with　modulated　abundant　highly　electronegative　F　atoms　distribution　reduces　the　water　adsorption　energy　and　oxidation　kinetics　of　Li13Si4@PFPE/LiF,　which　delivers　a　high　pre-lithiation　capacity　retention　of　84.39%　after　exposure　to　extremely　moist　air　(60%　relative　humidity).　Intriguingly,　a　LiF-rich　mechanically　stable　bilayer　SEI　is　constructed　on　anodes　through　a　pre-lithiation-driven　regulation　for　the　behavior　of　electrolyte　decomposition.　Benefitting　from　pre-lithiation　via　multifunctional　Li13Si4@PFPE/LiF,　the　full　cell　and　pouch　cell　assembled　with　pre-lithiated　anodes　operate　with　long-time　stability　of　86.5%　capacity　retention　over　200　cycles　and　superior　energy　density　of　549.9　Wh　kg-1,　respectively.　The　universal　multifunctional　pre-lithiation　additives　provide　enlightenment　on　promoting　large-scale　applications　of　pre-lithiation　on　commercial　high-energy-density　and　long-cycle-life　lithium-ion　batteries.