Separation　and　recovery　of　molybdenum　(Mo)　with　high　concentrations　from　spent　catalysts　is　a　strategy　for　avoiding　the　environmental　footprint　by　metal　mining　and　the　disposal　of　hazardous　wastes,　while　alleviating　resource　shortage.　In　this　paper,　a　method　for　constructing　a　binary　(SiO2-Na2O)/ternary　(SiO2-Na2O-B2O3)　glass　phase　extraction　(GPE)　system　to　selectively　extract　the　impurity　metal　ions　from　spent　catalysts　as　well　as　simultaneously　separate　and　recover　Mo　is　presented.　Based　on　experimental　studies　and　classical　molecular　dynamics　simulations,　compared　with　the　binary　glass　network,　99.4%　of　Al3+　and　Ni2+　in　spent　catalysts　were　extracted　in　a　more　stable　tetra-coordinated　form　at　a　lower　melting　temperature　(1200　degrees　C)　by　the　ternary　GPE　system　introducing　B2O3,　accompanied　by　Na2MoO4　precipitated　as　the　recovery　product.　The　recovery　efficiency　of　Mo　was　98.1%,　realizing　an　efficient　separation　and　short-process　recovery.　Moreover,　the　separation　of　Na2MoO4　melt　and　glassy　liquid　during　the　melting　process　was　visually　observed　online.　Therefore,　this　approach　of　constructing　glass　GPE　systems　for　the　one-step　separation　of　metals　during　the　melting　process　is　expected　to　contribute　to　the　sustainable　supply　of　critical　metals.