The　V2O5/TiO2　catalyst　is　the　most　concerned　NH3-SCR　catalytic　system　for　simultaneous　removal　of　NOx　and　chlorinated　volatile　organic　compounds　(Cl-VOCs).　There　is　an　urgent　need　to　develop　a　vanadia-based　catalyst　with　low　vanadium　loading　and　excellent　low-temperature　catalytic　performance.　In　this　work,　the　Pr　and　W　codoped　vanadia-based　catalysts　were　prepared　by　a　simple　impregnation　method.　After　the　doping　of　Pr　and　W,　the　vanadia-based　catalyst　exhibited　the　excellent　catalytic　activity　for　NOx　reduction　and　chlorobenzene　(CB)　oxidation.　The　more　abundant　polymeric　vanadyl　species　and　crystalline　V2O5　were　observed　on　the　PrV5W/Ti　catalyst,　which　are　contributing　to　NH3-SCR　and　CB　oxidation　activity.　The　redox　capability　and　the　amount　of　surface-active　adsorbed　oxygen　of　vanadia-based　catalyst　were　improved　markedly,　thus　promoting　NH3-SCR　and　CB　oxidation　reaction　on　PrV5W/Ti.　This　catalyst　is　promising　to　be　used　in　the　muti-pollutant　control　reaction　of　NOx　and　VOCs.