The　separation　and　recovery　of　tungsten　and　cobalt　from　cemented　tungsten　carbide　(WC-Co)　scraps　can　be　carried　out　by　adding　WO3　and　CoO　into　the　Na2WO4　molten　salt　to　simulate　the　calcination　of　WC-Co　scraps.　The　Raman　spectra　and　the　XRD　patterns　of　the　molten　salts　cooled　naturally　to　room　temperature,　and　the　predominance　diagram　of　Na-W-Co-O　system,　show　that　the　addition　of　CoO　reduced　the　concentration　of　Na2W2O7　in　the　molten　salt.　Molecular　dynamics　simulations　based　on　first　principles　indicated　the　following　reaction　mechanism:　WO42　+　WO3　-＞　W2O72　,　W2O72　+　O2-　-＞　2WO42　.　Electrochemical　cyclic　voltammetry　(CV)　and　square　wave　voltammetry　(SWV)　were　used　to　analyze　the　redox　behaviors　of　tungsten　and　cobalt　with　different　molar　ratios　of　WO3　and　CoO　in　the　molten　salts.　The　reduction　of　the　tungsten　ion　was　a　two-step　reaction,　W6+　-＞　W2+　-＞　W,　and　the　reduction　of　the　cobalt　ion　was　a　one-step　reaction,　Co2+　-＞　Co.　On　increasing　the　amount　of　added　CoO,　the　deposition　potential　of　tungsten　ions　shifted　towards　a　more　negative　potential,　while　the　deposition　potential　of　cobalt　ions　remained　unshifted.　Therefore,　W　coatings,　Co3W　alloys　and　Co　powders　were　obtained　by　selective　electrodeposition.