A highly active catalyst of cerium–tungsten–titanium mixed oxide was synthesized by introducing Ce4+ and H2O2 in the base sample of Ce20W10Ti100Oz–Ce3+. As a consequence, the NH3-SCR activity of Ce20W10Ti100Oz–Ce3+ is significantly improved as the additives of Ce4+ and H2O2 enlarge the Brunauer–Emmett–Teller (BET) surface area by refining its pore size. Meanwhile, the introduction of Ce4+ increases the Lewis acid sites of Ce20W10Ti100Oz–Ce3+ and decreases its low-temperature Brønsted acid sites. The further addition of H2O2 improves the Brønsted acid sites and dispersion of cerium/tungsten species, and thereby enhances the concentrations of the adsorbed oxygen (Oα) and the adsorbed oxygen $\lpar {\rm {O}^{\prime}}_{\rm \alpha} \rpar$ due to the activation of chemisorbed water on the surface of the catalyst. The addition of Ce4+ and H2O2 shows a synergistic promotional effect, which is due to the largest BET surface area and the highest concentrations of Oα or/and ${\rm {O}^{\prime}}_{\rm \alpha}$. Ce20W10Ti100Oz–Ce3+:Ce4+ = 17.5:2.5 + H2O2 exhibits the highest catalytic activity compared with the conventional ones (Fig. 5).