Spent　hydrofining/selective　catalytic　reduction　catalysts　generated　during　the　production　of　ultra-low-sulfur/nitrogen　fuel　are　considered　to　be　hazardous　wastes.　Furthermore,　the　sustainable　supply　of　critical　metal　resources　such　as　molybdenum　(Mo),　tungsten　(W),　nickel　(Ni)　and　vanadium　(V),　which　are　present　in　high　concentrations　in　spent　catalysts,　is　challenged　by　the　climate　emergency,　ore　depletion　and　inefficient　technologies　for　separating　metals.　Here,　glass　phase　extraction　is　proposed　as　a　novel　approach　for　simultaneously　separating　metals　and　obtaining　recovered　products　from　spent　hydrofining　catalysts　in　one　step.　By　constructing　a　glass　network　structure　that　satisfied　a　stable　coordination　environment　for　the　target　metal　ions,　99.82　%　of　the　Mo6+　was　“melt-melt”　separated　with　the　glass　phase　as　Na2MoO4,　while　the　extraction　efficiencies　of　Ni2+　and　Al3+　were　＞99.16　%.　The　separation　factors　βMo/Ni　and　βMo/Al　were　as　high　as　65812.95　and　71944.85,　respectively.　The　obtained　results　verify　this　method　as　a　valuable　synthetic　route　for　refractory　metal　salts　and　transition　metal　ion-doped　glass–ceramic　materials,　enhancing　the　prospect　of　achieving　full-component　resource　recovery　from　hazardous　wastes.　©　2023　Elsevier　B.V.