The nonselective catalytic reduction (NSCR) reaction and the catalytic oxidation of NH3 to NO (C-O reaction) simultaneously happened during the selective catalytic reduction (SCR) of NO with NH3 over V2O5-WO3/TiO2, especially at higher temperatures. There was an excellent linear relationship between the SCR reaction rate and gaseous NO concentration, and the intercept and slope can be used to describe the rate constant of NO reduction through the Langmuir-Hinshelwood mechanism and that through the Eley-Rideal mechanism, respectively. However, the NSCR reaction rate was nearly independent of gaseous NO concentration, and the reaction order of the C-O reaction with respect to gaseous NO concentration was much less than zero. According to the kinetic study, the relationship of the SCR performance (i.e., SCR activity and N-2 selectivity) with the key factors (for example V2O5 content, H2O effect, and reactant concentration) was built, which can be used to predict the SCR performance.