This work provides a simple approach of the F--assisted one-pot hydrothermal reaction to successfully synthesize Bi2WO6 hierarchical erythrocyte microspheres. The importance role of F- was systematically investigated by comparing different type of halogen ions, hydrothermal temperature and time. The possible growth mechanism of Bi2WO6 hierarchical structures was proposed. The hierarchical erythrocytes were formed through the well-ordered and oriented self-assembly of thin Bi2WO6 nanoplate primary subunits. F- ions were absorbed on Bi2WO6 nanoplate surface to suppress the nanoplate stack but to induce a self-assembly through the edge interaction of Bi2WO6 nanoplates into erythrocyte-like hierarchical microspheres superstructures. This erythrocyte structure narrowed the band gap energy and enhanced the visible-light photocatalytic activity of Bi2WO6. Moreover, superoxide radical anions and h(+) were revealed as the main active species responding for the RhB degradation on Bi2WO6 under visible light irradiation. (C) 2017 Elsevier B.V. All rights reserved.