Hierarchical nanosheet-based Bi2MoO6 microboxes are synthesized by a facile template-assisted strategy. MnCO3 microcubes are prepared as templates for the growth of Bi2MoO6 nanosheets and then etched by using HCl aqueous solution. In particular, the hierarchical Bi2MoO6 microboxes provide a large surface area, and facilitate visible-light absorption and charge separation, demonstrating efficient photocatalytic performance. This work highlights a new method to prepare hollow nanosheet-built Bi2MoO6 structures with high photocatalytic properties.