The invention provides a fire coal desulfurization and denitrification decoking additive and a preparation process thereof. The fire coal desulfurization and denitrification decoking additive comprises a coal dust additive, which is added to the fire coal, and a catalytic activator, which is added to a slurry tank of a desulfurization system; and the preparation process comprises the following steps of: first, adding sodium carbonate, magnesium oxide, silicon dioxide, zinc oxide, manganese dioxide, copper oxide and barium oxide in sequence and stirring the mixture for 20 minutes; and then adding active calcium oxide and ammonium bicarbonate, and stirring the mixture for 10 minutes; uniformly mixing the mixture to obtain the coal dust additive; first stirring the active calcium oxide, active aluminum oxide and caustic calcined magnesite for 15 minutes; and then adding active carbon and calcium ammonium nitrate, and uniformly stirring the mixture to obtain the catalytic activator. According to the invention, without changing the traditional boiler and desulfurization equipment as well as the process thereof, the user selects corresponding additive and catalytic activator provided by the invention according to physical and chemical indexes of the coal so as to produce coal-saving, desulfurization, denitrification and decoking effects. During using high sulfur coals, the desulfurization efficiency is obviously increased and the SO2 emission reduction reaches the standard.