Modulating　interfacial　electrochemistry　represents　a　prevalent　approach　for　mitigating　lithium　dendrite　growth　and　enhancing　battery　performance.　Nevertheless,　while　most　additives　exhibit　inhibitory　characteristics,　the　accelerating　effects　on　interfacial　electrochemistry　have　garnered　limited　attention.　In　this　work,　perfluoromorpholine　(PFM)　with　facilitated　kinetics　is　utilized　to　preferentially　adsorb　on　the　lithium　metal　interface.　The　PFM　molecules　disrupt　the　solvation　structure　of　Li+　and　enhance　the　migration　of　Li+.　Combined　with　the　benzotrifluoride,　a　synergistic　acceleration-inhibition　system　is　formed.　The　ab　initio　molecular　dynamics　(AIMD)　and　density　functional　theory　(DFT)　calculation　of　the　loose　outer　solvation　clusters　and　the　key　adsorption-deposition　step　supports　the　fast　diffusion　and　stable　interface　electrochemistry　with　an　accelerated　filling　mode　with　C　&　horbar;F　and　C　&　horbar;H　groups.　The　approach　induces　the　uniform　lithium　deposition.　Excellent　cycling　performance　is　achieved　in　Li||Li　symmetric　cells,　and　even　after　200　cycles　in　Li||NCM811　full　cells,　80%　of　the　capacity　is　retained.　This　work　elucidates　the　accelerated　electrochemical　processes　at　the　interface　and　expands　the　design　strategies　of　acceleration　fluorinated　additives　for　lithium　metal　batteries.　The　use　of　accelerating　additive　perfluoromorpholine　(PFM)　can　cause　disturbance　to　the　solvated　structure　and　increase　the　diffusion　coefficient　of　Li+.　In　addition,　the　preferential　adsorption　behavior　of　PFM　molecular　interface　can　accelerate　the　electrochemical　kinetics　process　of　the　interface,　regulate　the　deposition　behavior　of　Li+,　and　inhibit　the　growth　of　dendrites.　image