A novel method to synthesize the important lithium-ion battery electrolyte LiPF6 was developed and successfully applied in industrial-level production. In comparison with the conventional synthetic routes, the method employed CaF2 as the direct fluorinating agent instead of the corrosive and toxic HF. It was suitable for the surrounding environments of our company: the nearby fluorite mine could provide CaF2 at a relatively lower price, while the generated CaCl2 byproduct could be sold as the snowmelt agent for the surrounding highways, avoiding the accumulation of the solid wastes. Moreover, the product quality was obviously enhanced owing to the unique HF-free processes, which were environment-friendly and could even be performed near the national natural reserve. This work should be a good example of sustainable chemistry showing that the chemical industry could also be fully harmonious to the environments owing to the advanced green techniques.