In this paper, Bi2MoO6 microtubes (BMO-MTs) were obtained by a two-step fabrication route. By using the electrospun polyacrylonitrile (PAN) microfibers as structure-directing hard template and through ethylene glycol solvothermal method, polyacrylonitrile/Bi2MoO6 (PAN/BMO) hybrid microfibers with core-shell structures were prepared. Through heat treatment of the as-prepared PAN/BMO to remove the PAN core, Bi2MoO6 with tubes-structured were obtained. The thickness of BMO-MTs was controlled by changing the Bi2MoO6 loading percentage of PAN/BMO which could be obtained through ethylene glycol solvothermal process with precursor different concentration for the preparation of Bi2MoO6. And, the crystal structure and morphology of BMO-MTs strongly depended on the calcination temperature when heat-treating the as-prepared PAN/BMO. Photocatalytic tests show that the BMO-MTs possess a much higher degradation rate of Rhodamine B (RB) than that of Bi2MoO6 prepared by solid-state reaction and conventional P25. The improved photocatalytic performance could be ascribed to the hollow multi channelled structure and large surface area. The BMO-MTs could be reclaimed easily by sedimentation from the photocatalytic reaction solution due to the large length to diameter ratio of one-dimensional tubes structures. Moreover, such simple and versatile strategy can provide a general way to fabricate other tubes structures of Bi(III)-containing oxides, such as Bi2MoO6 and BiVO4 microtubes. (C) 2012 Elsevier B.V. All rights reserved.