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 NO_x conversion ratio beyond 90% at 440 °C and a remarkable resistance to poisoning in SO₂ and H₂O in the NH₃-SCR reaction.