Various nitrogen-doped hierarchical (BiO)2CO3 nanosheets architectures were synthesized by a facile one-step template-free hydrothermal method through controlling the hydrothermal temperature (HT). The as-synthesized samples were characterized by XRD, SEM, FT-IR, XPS, and UV-vis DRS. The photocatalytic activity of the samples was evaluated towards degradation of NO at ppb level in air under visible light (VIL). It was found that HT acted as a crucial factor in determining the morphology of the samples. The rosa chinensis-like, red camellia-like, and lamina-like of nitrogen-doped (BiO)2CO3 (N-BOC) micro-/nanostructures can be selectively fabricated under hydrothermal temperatures of 150, 180, and 210°C. The thickness of the nanosheets was in direct proportion to the increasing HT. Nitrogen-doping can extend the light absorption spectra of (BiO)3CO3 to visible light region and enhance the VIL photocatalytic activity. Especially, the red camellia-like N-BOC-180 exhibited the highest photocatalytic performance, superior to the well-known VIL-driven photocatalyst C-doped TiO2 and N-doped TiO2. The high photocatalytic performance of N-BOC was attributed to the synergetic effects of enhanced visible light absorption, multiple light-reflections between the nanosheets, and accelerated transfer of reactants and product. This research could provide new insights to the development of excellent photocatalyst with efficient performance for pollution control.