A multipollutant (Hg-0/NO/dioxin)-containing gas stream-generating system is developed to investigate the effectiveness of V2O5-WO3/TiO2 catalyst for multipollutant control. The results indicate that plate-type 1.52 wt% V2O5 performs much better than two other catalysts for oxidizing Hg-0. With a higher vanadium loading of 1.52 wt% V2O5, higher Hg-0 conversions (53-75%) are observed compared to 0.66 wt% V2O5 (45-68%) and 0.26 wt% V2O5 (32-63%) for simulated flue gas streams. In addition, the mercury oxidation activity significantly increases with increasing concentration of hydrogen chloride. For removal of PCDD/Fs, the results show that the removal efficiencies of PCDD/F congeners achieved with V2O5-WO3/TiO2 range from 50% to 65%. It is observed that the removal efficiency of highly chlorinated PCDD/Fs is slightly higher than that of low-chlorinated PCDD/Fs. Overall, plate-type catalyst of 1.52 wt% V2O5 shows the highest Hg-0/NO/dioxin conversion and reduction efficiency among three catalysts evaluated.