The method includes a pretreatment step during an operation of a boiler in which in a predetermined period of time before shutdown of the boiler, a part of combustion gas that has bypassed an economizer provided in a flue gas duct for flue gas from the boiler is supplied to an upstream of a NOx removal device having a NOx removal catalyst and mixed with the combustion flue gas from the economizer to generate mixed gas having a predetermined temperature equal to or higher than 360° C. (360° C. to 450° C.), the mixed gas is introduced into the NOx removal catalyst, thereby decomposing VOSO4 adhering to and accumulating on the NOx removal catalyst into V2O5.