Bi2WO6 photocatalysts has been extensively studied for its photocatalytic activity. However, few works have been conducted on hierarchical Bi2WO6 composite photocatalysts with specifically exposed facets. In this work, we report a facile method to synthesize BiOCl@Bi2WO6 hierarchical composite micro spheres. Bi2WO6 nanosheets with specifically exposed (0 2 0) facet were directly formed on the surface of BiOCl precursor microspheres via a controlled anion exchange route between BiOCl and Na2WO4. The visible-light photocatalytic activity of the BiOCl@Bi2WO6 heterojunction with exposed (0 2 0) facets (denoted as BiOCl@Bi2WO6) was investigated by degradation of Rhodamine B (RhB) and ciprofloxacin (CIP) aqueous solution under visible light irradiation. The experimental results indicated that the BiOCl@Bi2WO6 composite microsphere with intimate interfacial contacts exhibited improved efficiency for RhB photodegradation in comparison with pure BiOCl and Bi2WO6. The BiOCl@Bi2WO6 composite microsphere also shows high photocatalytic activity for degradation of CIP under visible light irradiation. The enhanced photocatalytic performance of BiOCl@Bi2WO6-020 hierarchical microspheres can be ascribed to the improved visible light harvesting ability, high charge separation and transfer. This work will make significant contributions toward the exploration of novel heterostructures with high potential in photocatalytic applications. (C) 2015 Elsevier B.V. All rights reserved.