Converting CO2 into high-valued chemicals with sunlight is regarded as a promising way to solve the impending energy and environmental crisis Development of efficient photocatalysts with suitable energy band gap, high stability and favorable structure is thus of very importance Herein, a novel hierarchical Bi2WO6 photocatalyst assembled by Bi2WO6 nanosheets with a hollow and rod-shaped appearance has been developed via a facile hydrothermal process Interestingly, we found that the hydrolysis of Bi(NO3)(3) in water can produce solid Bi6O5(OH)(3)(NO(O)3())5 3(H)O0 microrods which can be transformed to hollow-hierarchical B(i)2O(06) nanosheets by virtue of the Kirkendall effect The developed B(i)2O(06) nanosheets exhibit a 58 times higher specific surface area than that of bulk B(i)2O(06) and a remarkable enhancement in electrochemical performance such as photocurrent and charge transfer As a result, the hollow-hierarchical structured B(i)2O(06) photocatalysts achieve a high CH4 yield of 2. 6 pmol (-1) h1(,) 8 times higher than that of bulk Bi(2)O0(6) Moreover, the developed photocatalysts exhibit a high stability during the recycling experiments This work may present a new strategy to attain hierarchical structured photocatalysts with high activity and stability toward O0(2) reduction (c) 2018 Elsevier Inc All rights reserved.