hollow Bi₂WO₆ nanoflowers have been successfully synthesized by using PVP modified hydrothermal method, and their morphology and structure are characterized by XRD, SEM, TEM, PL and UV-vis analysis. A series of controlling experiments indicate PVP play an important role in the formation of the hollow hierarchical structure. Without adding PVP, the morphology of Bi₂WO₆ is the solid nanoplate. When a small amount of PVP is added, the surface of Bi₂WO₆ splits, and the hollow flowerlike morphology forms. The crystalline size of Bi₂WO₆ also slightly increases with PVP contents increasing. The as-prepared PVP-Bi₂WO₆ shows the improved photocatalytic activity under visible light irradiation. After investigated by PL spectra, the emission intensity of PVP assisted Bi₂WO₆ is weaker than that of pure PVP, which means the high-mobility of PVP-Bi₂WO₆ is obtained. PVP assisted Bi₂WO₆ nanoflower can be potentially used for practical waste water treatments.