Large　amounts　of　hazardous　fluorine-containing　solid　waste　(HFSW)　are　produced　globally　each　year.　Recycling　HFSW　not　only　conserves　valuable　F　resources　but　also　serves　as　a　crucial　step　towards　environmental　sustainability.　This　work　proposed　an　efficient　and　green　approach　for　F　removal　and　recovery　from　the　HFSW　using　a　mechanochemical　method.　The　results　showed　that　MgF2　component　in　the　HFSW　can　be　almost　completely　converted　to　NaF　and　Mg(OH)2　by　the　mechanochemical　force　with　NaOH　as　co-grinding　agent.　A　possible　NaOH　mechanochemical　decomposition　and　conversion　mechanism　of　MgF2　is　also　proposed　based　on　thermodynamics,　XRD,　TEM　and　DFT　calculations.　By　optimizing　the　mechanochemical　conditions,　such　as　NaOH　concentration　of　35　mol/L,　ball-to-material　ratio　of　10:1　g/g,　liquid-solid-ratio　of　1.8　mL/g,　mechanical　activation　speed　of　600　rpm,　and　mechanical　activation　time　of　150　min,　99.51　%　of　F　in　the　HFSW　can　be　leached.　Finally,　98.69%　purity　of　NaF　product　was　recovered　from　the　as-obtained　F-containing　leachate　through　N　235　extraction　and　evaporative　crystallization.　The　results　of　this　work　are　expected　to　provide　a　promising　solution　for　F　removal　and　recovery　from　HFSW.