The photocatalytic activity of bismuth oxyhalides largely depends on their morphologies and microstructures. In this work, hierarchically structured bismuth oxyiodide (BiOI) with tunable ratios of (110) and (001) facets are fabricated through a facile route combining solid-state reaction with subsequent hydrolysis at room temperature. The hierarchical structures endow BiOI with excellent visible-light photocatalytic performance for phenol degradation. Besides, the optimal ratio of (001) and (110) surfaces also plays an important role in enhancing the photocatalytic activity of BiOI. DFT calculation demonstrates that a surface heterojunction formed between (001) and (110) surfaces can improve the separation of electrons and holes on different surfaces and thus enhance the photocatalytic activity. (C) 2016 Elsevier Inc. All rights reserved.