Uniform erythrocyte-like Bi2WO6 hierarchical architecture constructed by ultrathin nanoflakes (similar to 4.4 nm) is firstly obtained via an anionic self-regulation strategy without employing any additives at a facile hydrothermal process. The unique hierarchical architecture exhibits high specific surface area and abundant mesoporous distribution, which can provide more reaction active sites and molecule transport channels. The novel structure also facilitates efficiently transfer and separation of charge carriers. In consequence, the photocatalytic activity and gas sensing property are obviously improved relative to the typical Bi2WO6 microsphere. This work extends the development of Bi2WO6 hierarchical architecture as well as launches a simple, eco-friendly and exemplificative strategy for constructing other Bi-based oxide hierarchical architecture. (C) 2014 Elsevier B.V. All rights reserved.