Efficient　electrochemical　dissolution　of　tungsten　carbide　is　crucial　to　obtain　an　efficient　recovery　of　cemented　carbide　via　molten　salt　electrolysis.　Based　on　the　interfacial　process,　the　dissolution　mechanism　of　tungsten　carbide　in　oxygen-containing　molten　salt　was　investigated　via　a　mass　loss　test,　electrochemical　tests,　and　first　principles　calculations.　Through　the　mass　loss　study,　it　was　found　that,　although　the　tungsten-carbon　bond　was　extremely　stable,　an　effective　electrochemical　dissolution　of　tungsten　carbide　could　also　occur　in　the　presence　of　oxygen　ions.　The　electrochemical　tests　demonstrated　that　an　increase　in　oxygen　ions　leads　to　a　continuous　substitution　of　chloride　ions　with　oxygen　ions　on　the　anode　surface.　These　oxygen　ions　are　further　converted　into　oxygen　atoms　under　the　action　of　an　electric　field.　The　oxygen　atoms　on　the　anode　surface　can　then　effectively　destroy　the　tungsten-carbon　bond　and　promote　mass　loss,　as　demonstrated　by　first　principles　calculations.　In　addition,　the　appearance　of　maximum　mass　can　be　related　to　the　saturation　of　the　electrostatic　adsorption　of　oxygen　ions.