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.