A dual-function catalyst, designated as Cu5-VWT, has been constructed for the synergistic removal of NO x and volatile organic compounds under complex coal-fired flue gas conditions. The removal of toluene, propylene, dichloromethane, and naphthalene all exceeded 99% (350 °C), and the catalyst could effectively block the generation of polycyclic aromatic hydrocarbons. Mechanistic studies have shown that Cu sites on the Cu5-VWT catalyst facilitate catalytic oxidation, while V sites facilitate NO x reduction. Thus, toluene oxidation and NO x reduction can proceed simultaneously. The removal of total hydrocarbons and nonmethane total hydrocarbons from 1200 m 3 ·h -1 real coal-fired flue gas by a monolithic catalyst were determined as 92 and 96%, respectively, much higher than those of 54 and 72% over a commercial VWT catalyst, indicating great promise for industrial application.