The flower-like, pinon-like and faceted nanoplates (BiO)(2)CO3 micro/nanostructures were fabricated by a onepot template-free method based on hydrothermal treatment of the aqueous mixture of bismuth citrate and sodium carbonate. The morphology of (BiO)(2)CO3 can be simply controlled by the reaction temperature. X-ray diffraction, scanning electron microscopy, UV vis diffuse reflection spectra, and photoluminescence spectra were applied to analyze the microstructures and properties of the samples. The flower-like and pinon-like (BiO)(2)CO3 superstructures were hierarchically self-assembled by nanoplates and showed increased light absorption owing to the multiple light reflection between the nanoplates. The thickness of nanoplates was increased with the increasing reaction temperatures due to the preferred growth along the (110) plane. The (BiO)(2)CO3 with various micro/nanostructures showed morphology-dependent photocatalytic activity toward removal of aqueous RhB. The as-prepared flower-like (BiO)(2)CO3 microspheres exhibited highest photocatalytic activity due to the large surface area, increased light absorption, enhanced charge carriers separation, and special architectures of hierarchical nanoplates microspheres, exceeding that of the P25. (C) 2013 Elsevier B.V. All rights reserved.