The development methods and development status of alternatives to chlorofluorocarbons (CFCs) were introduced in this review. Currently, developed alternatives to CFCs include hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFOs). Among them, HFOs have excellent environmental performance, which can be used to replace HFCs in the fields of refrigeration and foaming. The main synthetic routes of HFOs are summarized, and the best industrialization route is pointed out. However, the core patents of HFOs are monopolized by foreign developed countries, and HFOs have the risk of secondary pollution and flammability. Besides, the performance of HFOs is difficult to meet the application requirements in the fields of precision cleaning, high-end chip manufacturing process and high-voltage electrical insulation. Looking forward to the future development of CFCs substitutes, it is proposed that the future research focus will be: it is necessary to develop a new generation of alternatives to meet the country's major strategic needs so that our contry achieve precise replacement of CFCs in many fields.