The　unique　properties　of　fluorine-containing　organic　compounds　make　fluorine　substitution　attractive　for　the　development　of　pharmaceuticals　and　various　specialty　materials,　which　have　inspired　the　evolution　of　diverse　C-F　bond　activation　techniques.　Although　many　advances　have　been　made　in　functionalizations　of　activated　C-F　bonds　utilizing　transition　metal　complexes,　there　are　fewer　approaches　available　for　nonactivated　C-F　bonds　due　to　the　difficulty　in　oxidative　addition　of　transition　metals　to　the　inert　C-F　bonds.　In　this　regard,　using　Lewis　acid　to　abstract　the　fluoride　and　light/radical　initiator　to　generate　the　radical　intermediate　have　emerged　as　powerful　tools　for　activating　those　inert　C-F　bonds.　Meanwhile,　these　transition-metal-free　processes　are　greener,　economical,　and　for　the　pharmaceutical　industry,　without　heavy　metal　residues.　This　review　provides　an　overview　of　recent　C-F　bond　activations　and　functionalizations　under　transition-metal-free　conditions.　The　key　mechanisms　involved　are　demonstrated　and　discussed　in　detail.　Finally,　a　brief　discussion　on　the　existing　limitations　of　this　field　and　our　perspective　are　presented.　[Figure　not　available:　see　fulltext.]　©　2021,　The　Author(s).