Abstract: Taking a large domestic electrolytic aluminum enterprise as an example, the key links of fluoride production were analyzed and tested, the fluorine balance of the enterprise was constructed by material flow analysis method, and the distribution features of the characteristic pollutant fluoride in the electrolytic aluminum production process was studied. The results showed that apart from the overhaul slag of electrolytic cell, unorganized flue gas and carbon slag were the key points of fluoride emission in electrolytic aluminum production. The fluoride content of unorganized flue gas was 0.374 kg/t per unit product, which was about 3.7 times of that of organized emissions. The fluoride content in carbon slag was 6.347 kg/t, which was about 2.7 times of that in overhaul slag. In order to strengthen the fluoride risk prevention and control in the electrolytic aluminum industry, some suggestions were put forward starting from the whole production process, including effectively controlling the unorganized emissions by improving the gas collecting efficiency of electrolytic cells and controlling the smoke emissions scientifically, optimizing the smoke exhaust pipes of the electrolytic cells to improve the efficiency of organized flue gas treatment, controlling the water content of raw materials to reduce fluoride production at source, and strengthening the control of fluorine-containing solid wastes. Through these methods, the fluorine pollution caused by electrolytic aluminum enterprises to the surrounding environment could be reduced.