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Supported manganese vanadate catalysts for selective catalytic reduction of NOx by ammonia (NH3-SCR) with wide temperature window were fabricated by assistance of microwave. Vanadate dispersed well on the surface of TiO2, giving an enhanced activity in a wide temperature range. The activity over the catalyst at low temperatures enhanced as vanadate loading increased, deriving from the promoting redox property and the lowering stability of adsorbed NH3 species. The in situ DRIFT results indicated that NH3-SCR reaction over the well dispersed vanadate catalyst follow the “Eley-Rideal” (E-R) mechanism for the effective adsorption of NH3. The results showed the potential applications of this kind of catalyst for NOx elimination in some certain conditions.