The invention relates to the application of microwave and ultrasonic technologies in synthesizing tiotropium bromide anhydride, in particular to a method for preparing the refined product of a finished product, namely, tiotropium bromide anhydride through crystallization and recrystallization processes by using a crude product of tiotropium bromide prepared through bromization reaction after hydrolytic reaction of scopolamine hydrobromide under microwave function, substitution and coupling reaction of bromothiophene, magnesium, and oxalic acid dimethyl ester under the microwave function, and condensation reaction of scopine and thiophen methyl glycollate under the microwave function. Using the invention to prepare tiotropium bromide anhydride, not only the reaction time is short, the side reaction is less, and the yield rate is high in the room temperature condition, but also the product quality is stable, controllable, safe and effective.