Prevention of endogenous fires is a continuous preoccupation of the researchers of the National Institute of Safety in Mine and Explosion Protection (INSEMEX) Petrosani. A new direction has been taken in this regard since the 80 s based on the inhibition of oxidation phenomenon against the conventional one, based on the cooling effect of antipyrogenous substances. The research was founded on the new theories and hypotheses on self-oxidation of coals. The first successful trials we obtained with inorganic inhibitors of phosphate class, the methods of their application being also tested underground. Subsequent research broadened the range of inhibiting substances, superior results being obtained in laboratory renditions. The use of inorganic inhibitors widens the range of means and methods of self-heating/self-ignitions phenomena, resulting in the increase of safety in coal mine workings.