Fluorine　(F)　additives　could　enhance　lithium　(Li)　extraction　from　α-spodumene　without　phase　transformation　(typically　at　∼　1100　°C).　Fluorine　additives　participated　in　the　destruction　of　the　crystal　structure　of　α-spodumene　by　forming　HF　with　sulfuric　acid.　The　sulfuric　acid　was　employed　to　catalyze　the　destruction　of　the　α-spodumene　crystal　structure　and　convert　insoluble　fluorides　to　sulfates.　Residual　fluorine　mainly　existed　as　HF/F-　and　a　samll　amount　of　AlFx　after　acid　pre-leaching.　Based　on　different　boiling　points　of　HF-H2O　and　H2SO4-H2O　systems,　a　stepwise　heat　treatment　was　proposed　herein　to　recycle　F　and　avoid　lithium　loss　caused　by　coordination　with　F.　A　systematical　investigation　of　effects　of　different　factors　such　as　heating　temperature　(200–350　°C),　heating　time　(3–12　h),　initial　ratio　of　ore/H2SO4　(1:1,　1:2　g/mL)　and　different　heating　style　(directly　or　stepwise)　on　F　removal　was　conducted.　The　results　indicated　that　only　2.03%　of　F　remained　in　the　leaching　solution　after　the　stepwise　heat　treatment　for　an　ore/HF/H2SO4　ratio　of　1:3:2　g/mL/mL　at　120　°C　for　3　h　and　250　°C　for　3　h.　About　93.73%　of　Li　and　73.14%　of　Al　were　extracted　during　this　stepwise　heat　treatment.　More　importantly,　premiliary　separation　of　Li　and　Al　was　realized　due　to　the　formation　of　acid　insoluble　Al2(SO4)3,　which　was　conducive　to　the　subsequent　separation　and　purification　of　lithium　production.　©　2021　Elsevier　Ltd