The different compositions of Bi2MoO6 by tungsten substitution have been successfully synthesized via a facile hydrothermal process in the absence of a surfactant. All W-doped Bi2MoO6 samples were composed of nanosheets with similar orthorhombic Aurivillius layered structures. Bi2MoO6 samples show different phases varied with W content. For the Bi2MoO6 samples with the different n(w) values, their band gaps have changed obviously compared with Bi2MoO6 (2.69 eV) and Bi2MoO6 (2.75 eV). The Bi2MoO6 by tungsten substitution exhibited good photocatalytic activity in degradation of Rhodamine-B under 500 W Xe lamp light irradiation. When n(w) value is 0.5, the sample has the highest photocatalytic activity for RhB photodecomposition under visible light irradiation. It shows that photocatalytic activities of Bi2MoO6 samples by W substitution are relevant to nanosheet morphology and size, the intrinsic layered structure, band gap and the W content. (C) 2012 Elsevier B.V. All rights reserved.