A thin empty-shell bismuth tungstate hierarchical structure, which is composed of ultrathin nanosheets (∼14.0 nm), is constructed using the acid sculpture effect without any templates or surfactants by a facile hydrothermal process. It results in a large specific surface area and abundant pores through the inside and outside of the thin empty-shell, which shortens transport distance of organic molecules and provides plenty of reaction active sites for improving photocatalytic activity. The thin empty-shell bismuth tungstate hierarchical structure can more effectively remove colored RhB and colorless phenol in aqueous solutions relative to typical bismuth tungstate. The possible evolved mechanism of the thin empty-shell hierarchical structure and the photocatalytic reaction mechanism are discussed in detail.