The catalytic effects of inherent mineral matters on NOx emissions from coal combustion have been investigated by a thermo-gravimetric analyzer (TGA) equipped with a gas analyzer. The effect of demineralization and the individual effect of Na, K, Ca, Mg, and Fe on the formation of NOx are studied as well as the combined catalytic effects of Ca + Na and Ca + Ti. Demineralization causes more Fuel-N to retain in the char, and reduction of NOx mostly. But the mechanistic effect on NOx formation varies from coal to coal. Ca and Mg promote NOx emission. Na, K, Fe suppress NOx formation to different extents. The effect of transition element Fe is the most obvious. The combination of Ca + Na and Ca + Ti can realize the simultaneous control of sulfur dioxide and nitrogen oxides emissions.