The invention relates to a modification method of an SCR catalyst for removing chlorobenzene in flue gas by catalytic combustion and a catalyst. The method comprises the following steps of: S1, preparing a vanadium-titanium catalyst, and grinding the catalyst to obtain vanadium-titanium catalyst powder; S2, preparing a modified precursor and adding the modified precursor into a water solution to obtain a modified precursor solution which comprises one or more of manganese, chromium, copper, zirconium, niobium and molybdenum; S3, adding the vanadium-titanium catalyst powder into the modified precursor solution to form a mixed solution; and S4, drying and calcining the mixed solution in the step S3 so as to obtain a modified catalyst of which the active component is one or more of oxides of manganese, chromium, copper, zirconium, niobium and molybdenum. According to the method, the vanadium-titanium catalyst is modified, the catalytic combustion performance of the vanadium-titanium catalyst on chlorobenzene is enhanced while the NOx removal performance is guaranteed, then cooperative treatment of industrial furnace flue gas NOx and chlorobenzene is achieved, and the industrial furnace flue gas treatment cost can be greatly reduced.