In this study, highly effective B-doped, Ni-doped and B-Ni-codoped TiO2 microspheres photocatalysts were directly synthesized via an aerosol-assisted flow synthesis method. The resulting samples were characterized by XRD, SEM, TEM, UV-vis diffuse reflectance spectroscopy, nitrogen adsorption and XPS. The characterizations revealed hollow microspherical structure of the B-doped and B-Ni-codoped TiO2 photocatalysts, while the Ni-doped and undoped TiO2 products consisted of solid microspheres. It was found that the boron dopant was partially embedded into the interstitial TiO2 structure, existing in the form of Ti-O-B structure. The band gap was enlarged after the boron doping. However, both Ni-doped and B-Ni-codoped TiO2 samples showed obvious red shift in their absorption edges because of the Ni doping. The photocatalytic activities of these samples were evaluated on the photocatalytic removal of NO under simulated solar light irradiation. All the aerosol-assisted flow synthesized samples had much higher photocatalytic activities than P25 and the doped TiO2 microspheres exhibited enhanced photocatalytic activity than the undoped counterparts. More interestingly, the B-Ni-codoped TiO2 photocatalyst possessed superior photocatalytic activity to the as-prepared single doped TiO2 products. The enhanced photocatalytic activity was explained and the formation mechanisms of hollow and solid microspheres were also proposed on the basis of characterizations. We think this general method may be easily scaled up for industrial production of highly active microspherical photocatalysts for efficient NO removal under simulated solar light irradiation. Copyright © 2008 Elsevier B.V. All rights reserved.