A two stage hydrochloric acid leaching process is proposed for the treatment of lepidolite and recovery of alkali metals. The separation characteristics of aluminum and fluoride in the leachate were also determined. The transformation of lepidolite into silica-like residue was tentatively identified through X-ray diffraction measurements. The leach liquor was heated and concentrated and by evaporation to drive off to remove some of the hydrogen chloride and hydrogen fluoride from the acidic leachate, followed by cooling to deposit crystals. This yielded an overall hydrogen chloride and hydrogen fluoride removal of 25.4% and 2.52%, respectively. The main components of the crystals were aluminum and potassium chlorides, with small amounts of fluoroaluminate, polyaluminum chloride, and aluminum hydroxyfluoride. The crystals were calcined at 623 K, with a further 43.9% of hydrogen chloride and 4.33% of hydrogen fluoride being driven off and captured by adsorption equipment, which was beneficial for the subsequent separation of impurities. Investigation of the major mineral phases revealed that lower temperature calcination of the crystals tended to produce less-soluble polyaluminum chloride, aluminum hydroxyfluoride, fluoaluminate, and alumina. Water leaching of crystals after calcination at 623 K gave a leach liquor with 7.74 g/L of lithium, 0.15 g/L of aluminum and 0.25 g/L of fluoride. The fluoaluminate in the leach liquor led to the production of secondary precipitates after neutralization. The [AlFn]3-n species were partially dissociated to F− and Al(OH)4− at a strongly basic pH. The residual aluminum and fluoride concentrations were 0.01 g/L and 0.05 g/L, respectively, at the pH of 9. Since alkali chlorides such as lithium chloride are very soluble, there was less lithium loss during neutralization than in the corresponding sulfate system.