Lithium　and　its　associated　rubidium　are　regarded　as　the　strategic　metal　resource,　which　have　a　wide　use　in　many　commercial　products.　Nowadays,　the　continuing　growth　in　demand　for　Li　resources,　propelling　the　object　of　industrial　exploitation　will　focus　on　low-grade,　complex　minerals　composition　and　unwieldy　ores.　Zinnwaldite　has　received　increasing　attention　as　a　potential　lithium-containing　resource　in　recent　years.　However,　there　are　a　lack　of　effective　extraction　processes　for　zinnwaldite.　Hence,　this　paper　proposes　an　effective　method　to　extract　metal　cleanly　and　efficiently　from　zinnwaldite　by　using　CaO　and　B2O3　as　thermal　activation　additives　and　H2SO4　as　the　leaching　agent.　The　results　showed　that　the　destruction　of　Fe-O　and　Si-O-Si　bonds　led　to　increased　extraction　efficiency.　The　breathing　vibrations　of　oxygen　atoms　symmetric　in　4-　and　3-membered　rings　and　Si-O　symmetric　stretch　could　influence　the　Li　separation　from　silica　skeleton.　Ultimately,　the　91.32　%　Li,　93.09　%　Rb,　81.14　%　Fe,　95.00　%　Al　and　71.12　%　K　were　recovered　under　the　optimal　conditions.　Meanwhile,　about　10　%　F　escaped　into　the　air　during　thermal　activation　and　the　concentration　of　F　in　the　leaching　solution　was　lower　than　2　mg/L.　The　use　of　B2O3　provides　a　valuable　reference　for　the　efficient　and　clean　treatment　of　lepidolite　using　the　salt　roasting　method.　©　2024