As　metal　additive　manufacturing　(MAM)　technology　is　booming　in　the　aerospace　sector,　alternatives　to　the　traditional　production　methods　of　metals　such　as　mining,　processing,　and　refining　with　severe　emissions　are　urgently　needed.　This　study　proposed　a　closed-loop　route　for　efficient　recovery　of　molybdenum　(Mo)　and　value-added　reuse　of　tungsten　(W)　from　Cr–Co–Ni–Mo–W　alloy　waste　in　MAM.　The　results　showed　that　the　leaching　efficiency　of　Mo　and　W　reached　99.3%　and　99.9%,　respectively,　using　the　dual　chemical-physical　means　of　mixed-alkali　roasting　and　leaching　by　microwave　heating,　while　the　discharge　of　waste　liquor　containing　Cr6+　was　reduced.　Leaching　kinetic　studies　revealed　that　the　metal　leaching　process　was　controlled　by　chemical　reaction　mechanism.　Moreover,　the　10%N1923　(primary　amine)–5%TRPO　(tri-alkyl　phosphine　oxide)–kerosene　extraction　system　exhibited　a　synergistic　extraction　effect　on　Mo　and　W.　After　purification,　Mo　was　recovered　as　Mo　powder　for　MAM.　Simultaneously,　the　recovered　product　of　W,　MnWO4,　was　applied　as　a　photocatalytic　material　with　excellent　degradation　of　methylene　blue　dye.　Ultimately,　the　proposed　method　obtained　recovery　efficiencies　of　98.4%　and　99.3%　for　Mo　and　W,　respectively,　achieving　efficient　and　environmentally-friendly　reuse　of　these　key　metals.　©　2023　Elsevier　Ltd