Modulating vanadia-based metal oxides is one of the effective methods for designing difunctional catalysts for simultaneous control of NOx and chlorobenzene (CB) from the emissions of industrial sources. Excessive NH3 adsorption and polychlorinated species accumulation on the surface are the primary issues poisoning catalysts and reducing their lifetime. Herein, Sb is selected as an NH3 adsorption alleviator and polychlorinated species preventor dopant on V2O5-WO3/TiO2. The catalyst exhibits an excellent performance for total NOx and 90% CB conversions at 300-400 °C under a gas hourly space velocity (GHSV) of 60,000 mL g-1 h-1. The HCl and N2 selectivities are maintained at 90 and 98%, respectively. The anti-poisoning ability could be attributed to the generated V-O-Sb chains on the surface: the band gap of vanadium is narrowed and the electron capability is strengthened. The above variation weakens the Lewis acid sites and blocks the electrophilic chlorination reactions of the catalyst surface (formation of polychlorinated species). In addition, oxygen vacancies on Sb-O-Ti also increase: the ring opening of benzoates is accelerated and NH3 adsorption energy is weakened. The above variation lowers the energy barriers of C-Cl cleavage even under NH3 pre-adsorption models and enhances NOx reduction thermodynamically and kinetically.