Rose-like monodisperse hierarchical (BiO)(2)CO3 hollow microspheres are fabricated by a one-pot template-free method for the first time based on hydrothermal treatment of ammonia bismuth citrate and urea in water. The microstructure and band structure of the as-prepared (BiO)(2)CO3 superstructure are characterized in detail by X-ray diffraction, Raman spectroscopy, Fourier transform-infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, N-2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The monodisperse hierarchical (BiO)(2)CO3 microspheres are constructed by the self-assembly of single-crystalline nanosheets. The aggregation of nanosheets result in the formation of three dimensional hierarchical framework containing mesopores and macropores, which is favorable for efficient transport of reaction molecules and harvesting of photo-energy. The result reveals the existence of special two-band-gap structure (3.25 and 2.0 eV) for (BiO)(2)CO3. The band gap of 3.25 eV is intrinsic and the formation of smaller band gap of 2.0 eV can be ascribed to the in situ doped nitrogen in lattice. The performance of hierarchical (BiO)(2)CO3 microspheres as efficient photocatalyst are further demonstrated in the removal of NO in indoor air under both visible light and UV irradiation. It is found that the hierarchical (BiO)(2)CO3 microspheres not only exhibit excellent photocatalytic activity but also high photochemical stability during long term photocatalytic reaction. The special microstructure, the high charge separation efficiency due to the inductive effect, and two-band-gap structure in all contribute to the outstanding photocatalytic activities. The discovery of monodisperse hierarchical nitrogen doped (BiO)(2)CO3 hollow structure is significant because of its potential applications in environmental pollution control, solar energy conversion, catalysis and other related areas. (C) 2011 Elsevier B.V. All rights reserved.