Molten　salt　electrolysis　is　an　innovative　technology　applied　to　recover　tungsten　from　the　scrap　of　cemented　carbide,　which　enables　the　realization　of　energy　saving　and　consumption　reduction　goals.　Currently,　numerous　studies　have　focused　on　the　molten　salt　electrolysis　of　chlorine　salt　systems,　but　still　face　challenges　including　low　electrolysis　efficiency　and　salt　volatilization.　Here,　we　propose　to　employ　the　FLiNaK　molten　salt　system　for　recovering　tungsten　from　the　scrap　cemented　carbide　and　analyze　the　feasibility　of　the　dissolution　of　WC　occurring　at　the　anode　from　the　perspective　of　thermodynamics　and　electrochemical　polarization　curves.　Moreover,　the　influence　of　electrolysis　temperature　on　the　dissolution　of　the　anode　is　also　investigated　and　the　productions　are　identified　as　nano-flake　tungsten　powder　by　characterizing　the　cathode　product　using　XRD,　SEM,　EDS,　and　XPS.　A　two-step　reduction　mechanism　of　W　ions　was　analyzed　by　electrochemical　means　such　as　CV,　SWV,　etc.,　and　the　ionic　groups　stabilized　by　W6+　and　W4+,　and　F−　in　the　molten　salts　were　deduced　to　be　WF33+　and　WF3+　by　DFT　simulation　calculations.　This　work　provides　new　guidance　for　the　application　of　molten　salt　electrolysis　in　the　recovery　of　tungsten　from　scrap　cemented　carbide.　©　2024　Elsevier　Ltd