<p>With the rapid development of China’s aluminum electrolyte industry, a large amount of lithium–aluminum electrolytes are being discarded, leading to environmental pressure and wastage of lithium resources. This study proposes an effective method for extracting lithium from lithium–aluminum electrolytes and preparing it into lithium carbonate. The method is divided into four steps: Aluminum salt is added during roasting to transform the phase of lithium, followed by dissolution of lithium into the solution, and subsequent addition of sodium hydroxide and sodium carbonate solutions to remove impurities (F, Al, Ca), resulting in the preparation of lithium carbonate. Under optimal conditions, the lithium content was reduced from 1.78 wt.% to 0.029 wt.% and a leaching efficiency of 98.9% was achieved; the obtained lithium carbonate purity is 98.6% and the recovery of Li was 71.14% for the entire process. Aluminum fluoride and calcium carbonate, which can be used in industrial production, were also obtained. Overall, this study provides an efficient and viable solution for treating waste lithium-rich aluminum electrolytes, contributing to resource recovery and environmental protection.</p> Graphical Abstract <p></p>