Abstract A series of monolithic V2O5–WO3/TiO2 catalysts with different vanadium and tungsten supported amounts were synthesized via coated mixed colloid, which contained certain amount of activity component. The layer coated on the ceramic substrate obtained a homogeneous distribution with strong adhere force and deep penetration with the collosol dipping into honeycomb ceramic according to the result of ultrasonic measurement and scanning electron microscopy (SEM). The new coating procedure was benefit to form highly dispersed species and generated more active site based on the result of XRD and Raman. In contrast with blank ceramic, monolithic catalyst possessed larger specific surface area and appropriate ratio of macrospore and microspores. X-ray photoelectron spectroscopy (XPS) confirmed the co-existence of pentavalent vanadium and tetravalent vanadium in the catalyst, which was favorable for NH3-SCR reaction. The monolithic catalyst exhibited desirable activity with the NOx conversion ratio beyond 90% at 440 °C and a remarkable resistance to poisoning in SO2 and H2O in the NH3-SCR reaction.