The selective catalytic reduction (SCR) of NO with NH3 was systematically investigated over a series of supported vanadia catalysts to obtain additional insight into this important industrial reaction, The influence of surface vanadia coverage, promoters (surface tungsten oxide, niobium oxide, and sulfate species), and the specific oxide support (TiO2, Al2O3, and SiO2) was examined, The molecular structures of the surface metal oxide species were determined by in situ Raman spectroscopy, and the corresponding surface acidity properties were monitored with infrared spectroscopy employing pyridine adsorption, The redox properties of the surface metal oxide species were probed with the sensitive methanol oxidation reaction and temperature-programmed reduction. The SCR reactivity of the various catalysts was determined over a wide temperature range, The current findings suggest that a dual-site (a surface vanadia redox site and an adjacent nonreducible metal oxide site) mechanism is required for the efficient selective catalytic reduction of NO with NH3 over supported vanadia catalysts, The SCR reaction is sensitive to the immediate environment of the surface vanadia species : overall surface coverage of the metal oxide overlayer (factor of 5 in turnover frequency), nature of adjacent surface metal oxide species (factor of 10 in turnover frequency) and oxide support ligands (factor of 3 in turnover frequency). The SCR reaction, however, does not appear to depend on the specific structure of the surface vanadia species, The SCR selectivity toward N-2 formation also varies with the immediate environment of the surface vanadia species, The selectivity depends on the specific oxide support (TiO2 > Al2O3 > SiO2), temperature (decreases at higher temperature due to oxidation of NH3 and NO to N2O), and surface concentration of redox sites (decreases with the concentration of pairs of redox sites), The SCR reaction is not related to the properties of the terminal V=O bond since in situ Raman studies during SCR, employing V=O-18, demonstrate that this bond is relatively stable under reaction conditions (possessing a lifetime that is similar to 10 times the characteristic reaction time), Thus, the bridging V-O-support bond appears to be involved in the rate-determining step.