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　2　O　3　as　thermal　activation　additives　and　H2SO4　2　SO　4　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　2　O　3　provides　a　valuable　reference　for　the　efficient　and　clean　treatment　of　lepidolite　using　the　salt　roasting　method.