Formation of dioxins in flue gases is inhibited by contacting the flue gas with at least one of sodium phosphite, calcium phosphate, sodium hypophosphite, and calcium as reducing agents preferably at a temperature in the range of from 150° C. to 850° C. Hydrogen chlorides are also rendered harmless by the contact with the reducing agent. Also, metal ions contained in the fly ash of the flue gas are reduced to metals to reduce the occurrence of dissolution of the metals in subsequent treatment of the fly ash.