Background:　The　separation　of　tungsten　and　molybdenum　has　always　been　a　significant　challenge.　Metal　organic　frameworks　(MOFs)　has　potential　to　solve　the　problem.　In　this　study,　the　adsorption　and　separation　performance　of　UiO-66　for　tungsten　and　molybdenum　and　adsorption　mechanism　were　investigated.　Methods:　UiO-66　was　synthesized　by　solvothermal　method.　The　physical　and　chemical　properties　of　UiO-66　and　adsorption　mechanism　were　characterized　and　analyzed　by　XRD,　SEM-EDS,　FT-IR,　Zeta-potential,　XPS　and　thermodynamic　analysis,　the　adsorption　and　separation　performance　of　Mo/W　using　UiO-66　were　evaluated　by　ICP-OES.　Significant　findings:　UiO-66　with　uniform　pore　size　could　be　obtained　under　the　conditions　of　crystallization　for　24　h　at　180　°C.　This　study　revealed　superior　Mo/W　separation　performance　under　acidic　conditions,　where　the　adsorption　capacity　for　Mo　(QMo)　of　UiO-66　was　219.4　mg⋅g−1　and　the　highest　separation　factor　(βMo/W)　was　52.3.　It　was　found　that　the　mechanism　involved　the　effect　of　pore　size,　electrostatic　attraction　and　the　metal　point　Zr　had　stronger　affinity　for　Mo.　This　material　was　expected　to　serve　as　an　eco-friendly　and　reusable　adsorbent　for　separation　of　tungsten　and　molybdenum　in　resource　recovery,　aiming　for　high-quality　regeneration　of　both　metals.　©　2024　Taiwan　Institute　of　Chemical　Engineers