Three-dimensionally ordered macroporous Bi₂WO₆ (3DOM Bi₂WO₆) with mesoporous walls was firstly realized by a hard template synthesis method. The commercially available bismuth nitrate and phosphotungstic acid were used as the precursors to prepare the 3DOM Bi₂WO₆ sample without introducing other complex agents. The as-prepared 3DOM Bi₂WO₆ was composed of periodically arranged Bi₂WO₆ hollow spheres with a diameter of about 90 nm. Because of its particular ordered macroporous and mesoporous structure, the 3DOM Bi₂WO₆ exhibited excellent photocatalytic activity on the degradation of phenol and aqueous ammonia under irradiation from simulated sunlight. Its photocatalytic activity is much higher than that of the Bi₂WO₆ samples prepared by hydrothermal synthesis (HR) and solid-state reaction (SSR) methods. This work provides a simple way to prepare bismuth-based 3DOM multiple metal oxides with excellent performance.