Much more attentions are being devoted to high performance energy storage and conversion devices to conquer global warming issue and energy crisis. Lithium-ion battery, the most promsing device, is composed of anode, cathode, separator and electrolyte. Note should be highlighted that the performance of battery is determinded by electrolyte, espcially the safety issue. The demand of lithium-ion batteries and their electrolytes is growing rapidly with the rapid development of new energy vehicles recently. Lithium hexafluorophosphate (LiPF6) crystal is a white crystal with trigonal crystallographic structure. It is the key electrolyte material for Li-ion batteries. LiPF6 is combustible, corrosive and of poor thermal stability. Therefore, some toxic and corrosive precursors are employed, and their synthesis is required to be conducted within an anhydrous and anaerobic environment. Furthermore, many high temperature and low temperature treatments are involved in the synthetic procedure. Therefore, it is a huge challenge to produce high-purity LiPF6 crystals with an electronic grade in an industrial-scale. Fortunately, some industrial processes have been developed successfully by domestic enterprises even there is still some room for improving them. Here, the synthetic methods of LiPF6 and the domestic large-scale production processes are reviewed with the hope of providing some knowledge for future upgrade of the industrialized LiPF6 processes and a guideline for developing new synthetic routes. This review will concentrate on the development and intrinsic correlation among market demand of lithium-ion battery, role of electrolyte in lithium-ion battery, LiPF6 industrialized production procedures, and planned incremental capacity. In addition, the perspectives of potential electrolyte are summarized on basis of the progress of high-capacity and high-voltage electrode materials. There is no doubt that the future emphasis should be paid to the optimization of process, true demand of market, novel lithium salt, fluoridized solvents, and green techniques.