Low energy consumption and environmentally friendly recycling methods can extract high-added value and high-demand elements from retired waste fluorinated aluminum electrolytes (RWE-Al), which is crucial for alleviating resource shortages and environmental hazards. This study aims to develop a method for recovering fluorine and aluminum from RWE-Al through calcium leaching transformation combined with acid leaching. Compared to the traditional high-temperature roasting transformation and high-concentration alkali-metal-salt leaching process, this new process only involves one step of low-temperature leaching, purification of fluorine, carbonization of excess calcium, and evaporation extraction of aluminum, avoiding the generation of high energy consumption and secondary hazardous waste (F-containing liquid/ residue). Fluorine and aluminum are effectively separated and purified with extraction rates exceeding 96%. The effects of leaching temperature, CaO addition coefficient, liquid–solid ratio, and leaching time on the leaching process were systematically studied. The effects of acid concentration, liquid–solid ratio, time, and temperature on the acid-leaching process were also investigated. In summary, the comprehensive utilization of RWE-Al by this new process has proved to be feasible.