The pure beta-Bi2O3 and fluorine-doped beta-Bi2O3 rod-like microstructures were successfully prepared by a facile solid-state chemical reaction process. The composition, structure and morphology of the samples were determined by XRD, EDS, SEM, TEM, HRTEM, XPS and PL. Photocatalytic activities of all samples were investigated via the degradation of methyl orange (MO) under the irradiation of visible light. The fluorine-doped beta-Bi2O3 rods exhibited higher photocatalytic activities than the pure beta-Bi2O3 rod-like structures and commercial sample. The 82% MO can be degraded, by the fluorine-doped beta-Bi2O3 rods after irradiation for 2 h under visible light, which is 2-3 times higher than that of counterparts. The enhanced properties of the fluorine-doped samples attribute to their higher separation efficiency of electron-hole pairs and strong oxidation potential of valance band holes. The results show that the as-prepared rod-like fluorine-doped beta-Bi2O3 materials are potential candidates for photocatalysts irradiated by visible light. (C) 2016 Elsevier B.V. All rights reserved.