The invention discloses an ozone-assisted method for catalytic decomposition of volatile organic pollutants in high-temperature flue gas. According to the invention, ozone gas is introduced into a fixed bed reactor of a catalytic reaction. According to the catalyst in the fixed bed reactor, carbon nano-tubes, activated carbon, titanium dioxide, silica, or a composition thereof is adopted as a carrier; and Mn2O3, MnO2, CeO2, CuO, Cu2O, V2O5, Fe2O3, FeO, or a composition thereof is adopted as an active component. The active component accounts for 1-50% of total mass of the catalyst. The concentration of the introduced ozone gas is in a range of 0.1-50mg / L. According to the invention, a strong oxidant ozone is introduced in a catalytic decomposition process, such that active oxygen in the system is increased, catalytic decomposition of pollutant molecules is promoted, catalytic decomposition efficiency of the catalyst upon the volatile organic pollutants is substantially improved, and carbon dioxide selectivity is greatly improved. Therefore, an optimal effect of volatile organic pollutant low-temperature catalytic decomposition is achieved.