Chlorination roasting was used to extract lithium as lithium chloride from β-spodumene. The roasting was carried out in a fixed bed reactor using calcium chloride as chlorinating agent. The mineral was mixed with CaCl2 on a molar ratio of 1:2. Reaction temperature and time were investigated. The reactants and roasted materials were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD) and atomic absorption spectrophotometry (AAS). The mineral starts to react with CaCl2 at around 700°C. The optimal conditions of lithium extraction were found to be 900°C and 120min of chlorination roasting, under which it is attained a conversion degree of 90.2%. The characterization results indicate that the major phases present in the chlorinating roasting residue are CaAl2Si2O8, SiO2, and CaSiO3.