Mesoporous TiO2 microspheres composed of carbon-coated anatase nanocrystals w ith exposed {0 0 1} facets (TiO2(0 0 1)/C) have been successfully synthesized by a one-pot hydrothermal strategy in the presence of glucose and hydrofluoric acid (HF). It is demonstrated that the presence of HF promotes the growth of anatase nanocrystal with {0 0 1} facet exposure, while glucose induces TiO2 {0 0 1} nanocrystals to assembly into mesoporous TiO2 microspheres, as well as acts as carbon source in the formation of carbonaceous layer deposited on the TiO2 grains via C-O-Ti bond. The TiO2(0 0 1)/C microspheres show an excellent visible-light driven photocatalytic performance for the degradation of methyl blue. These results provide insight into the preparation, assembly and modification of TiO2 nanocrystals with active facets for potential application in environment protection. (C) 2013 Elsevier B.V. All rights reserved.