The destruction of the ozone layer in the atmosphere caused by industrially synthesized CFCs has aroused greatest concerns from the international society, but the CFCs formed from burning of coal containing fluorine have not been recognized by the world yet. In the present study, we condensed the gas through cold traps and used the GC-MS to measure the gas composition, and found that the content of CFC-12 in the smog from coal combustion was significantly higher than the background value of the local atmosphere. This proves that CFC-12 is formed in the process of coal combustion. This paper discusses a new source of non-synthesized CFCs.