Separation　of　tungsten　(W)　and　molybdenum　(Mo)　is　a　key　challenge　for　the　efficient　and　high-value-added　utilization　and　recycling　of　W　and　Mo　resources.　The　clean　and　recyclable　separation　technology　has　been　the　research　focus　in　this　field.　To　improve　the　effectiveness　of　W-Mo　adsorption　and　separation　and　avoid　sulfurization　in　the　ion　exchange　method,　a　functional　polytertiary　amine　macroporous　resin　(TA12-MR)　was　designed　and　prepared　first　time.　Optimal　synthesis　conditions　were　determined　by　optimizing　preparation　time,　temperature,　and　modifier　addition,　FTIR,　XRD,　SEM　and　BET　characterizations　revealed　that　TA12-MR　exhibited　enriched　amine　groups,　dense　structure　and　abundant　pores.　After　optimizing　the　adsorption　conditions,　QW　reached　743.6　mg·g−1,　βMoW　reached　20.1　at　pH　=　7.4,　T　=　25　°C,　t　=　4　h,　n(CTAB)/n(Mo)　=　0.5).　The　adsorption　isotherms　and　kinetics　fitting　results　indicated　that　the　adsorption　of　W　and　Mo　was　a　monolayer　spontaneous　chemically　adsorption.　The　mechanism　was　found　to　be　a　combination　of　electrostatic　adsorption　and　chemisorption.　Firstly,　W　migrated　near　N　which　on　TA12-MR,　followed　by　HWO4−　replaced　Cl−　for　ion　exchange　and　coordinated　with　N.　The　adsorption　property　remained　high　with　QW　=　849　mg·g−1,　QMo　=　85　mg·g−1,　after　ten　adsorption–desorption　cycles.　It　is　an　environmentally　friendly　and　high　recyclable　method　without　sulfurization　and　H2S　generation.　TA12-MR　is　expected　to　be　a　clean,　efficient,　reusable,　and　green　material,　which　can　be　applied　to　the　efficient　separation　and　comprehensive　recovery　of　W　and　Mo　secondary　resources,　to　provide　support　for　solving　the　problem　of　W-Mo　separation.　©　2023　Elsevier　B.V.