Regulating vanadia-based oxides has been widely utilized for fabricating effective difunctional catalysts for the simultaneous elimination of NO x and chlorobenzene (CB). However, the notorious accumulation of polychlorinated species and excessively strong NH 3 adsorption on the catalysts lead to the deterioration of multipollutant control (MPC) activity. Herein, protonated sulfate (-HSO 4 ) supported on vanadium-titanium catalysts via a preoccupied anchoring strategy are designed to prevent polychlorinated species and alleviate NH 3 adsorption for the multipollutant control. The obtained catalysts with -HSO 4 modification achieve an excellent NO x and CB conversion with turnover frequency values of ∼ 3.63 and 17.7 times higher than those of the pristine, respectively. The protonated sulfate promotes the formation of polymeric vanadyl with a higher chemical state and d-band center of V. The modulated catalysts not only substantially alleviate the competitive adsorption of multipollutant via the "V 3d-O 2p-S 3p" network, but also distinctly strengthen the Brønsted acid sites. Besides, the introduced proton donor of the -HSO 4 connecting polymeric structure could markedly reduce the reaction barrier of breaking the C-Cl bond. This work paves an advanced way for low-loading vanadium SCR catalysts to achieve highly efficient NO x and CB oxidation at a low temperature.