An　effective　method　using　hydrofluoric　and　sulfuric　acid　was　proposed　to　enhance　the　leaching　of　lithium　from　α-spodumene,　without　calcination　that　is　subjected　to　1000°C　for　phase　transformation.　The　thermodynamic　feasibility　of　the　reactions　was　firstly　verified.　Dissolution　conditions　were　tested　to　maximize　the　leaching　efficiency　of　lithium　and　with　efficient　utilization　of　hydrofluoric　acid　(HF)　served　as　evaluation　criteria.　The　results　showed　that　96%　of　lithium　could　be　transferred　into　lixivium　with　an　ore/HF/H2SO4　ratio　of　1:3:2　(g/mL/mL),　at　100°C　for　3　h.　Due　to　the　fact　that　HF　molecules　were　the　main　reaction　form,　the　dissolution　behaviors　were　theoretically　represented　and　investigated　by　dissolution　in　HF/H2SO4.　When　combined　with　chemical　elements　analyses　and　characterizations,　the　results　of　the　dissolution　behaviors　revealed　that　α-spodumene　and　albite　were　preferentially　dissolved　over　quartz.　Insoluble　fluoroaluminates,　such　as　AlF3,　cryolite　(Na3AlF6)　and　cryolithionite　(Na3Li3Al2F12),　were　generated　and　might　be　further　partially　dissolved　by　H2SO4.　Fluorosilicates,　such　as　K2SiF6,　Na2SiF6,　or　KNaSiF6,　were　also　generated　as　a　part　of　the　insoluble　residues.　This　work　provides　fundamental　insight　into　the　role　of　HF/H2SO4　played　in　the　dissolution　of　α-spodumene,　and　sheds　light　on　a　novel　and　promising　process　to　efficiently　extract　lithium.　©　2017　by　the　authors.