The　ionic　structure　of　poly(heptazine　imides)　has　a　strong　implication　in　photocatalytic　hydrogen　generation.　From　numerous　reports,　it　is　evident　that　these　materials　are　also　superior　to　covalent　carbon　nitrides　in　various　organic　transformations.　However,　the　reason　has　been　remaining　vague.　Herein,　we　report　the　design　of　a　molten-salt　carbon　nitride　(MCN)　featuring　ionic　structure　represented　by　negatively　charged　organic　polymeric　scaffold　and　K+　counterions　and　application　of　this　material　as　the　photocatalyst　in　synthesis　of　pharmaceutically　relevant　fluorinated　heterocycles　under　visible　light　under　the　redox　neutral　conditions.　K+　ions　serve　as　the　sites　for　sorption　of　ethyl　bromodifluoroacetate,　while　the　electronically　excited　state　of　MCN　acts　as　the　single　electron　transfer　agent,　enabling　generation　of　difluoroalkyl　radicals　from　the　substrate.　Combination　of　these　two　features　endows　a　material　that　outperforms　homogeneous　photocatalysts　and　covalent　carbon　nitrides.　Our　protocol　expands　the　application　of　carbon　nitrides　in　synthesis　of　organic　compounds　with　complex　structure　and　provides　fresh　perspectives　on　the　factors　contributing　to　the　enhanced　photocatalytic　efficiency　of　poly(heptazine　imides).　©　2024　The　Authors.　Published　by　American　Chemical　Society.