Processing spodumene for lithium is challenging as it requires a high temperature transformation of the natural α-monoclinic form to β-tetragonal form, usually followed by acid baking and digestion. This three-step extraction process requires significant heat energy, acid, process complexity and residence time, leading to both operating and capital costs. An approach which helps to eliminate this challenge will therefore be a milestone in processing spodumene. This study, thus, investigates a direct chlorination of α-spodumene using calcium chloride followed by water leaching of the residue to recover lithium, which reduces the energy requirement and number of unit operations. HSC Chemistry software was used to simulate the process using both phases (α and β) of the mineral up to 1100 °C prior to experimental investigation. The α-form was the only polymorph identified in residues after leaching, suggesting that the extraction is directly from the α-phase. However, an initial formation of a metastable β-form followed by a fast synthesis of lithium chloride from it is also suspected. Under optimal conditions of calcium chloride/spodumene molar ratio of 2.0, and 1000 °C treatment for 60 minutes, almost 90 percent lithium chloride was extracted and 85 percent was recovered to the leach solution with the remainder exiting with the off-gas. An apparent activation energy of about 122 ± 6 kJ mol⁻¹ was obtained at temperatures ranging from 800 to 950 °C during the process.