High activity hexagonal-BN (h-BN)/TiO2 composite photocatalysts were prepared by ball milling method. The structural and optical properties of the samples were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectra (DRS), and fluorescence emission spectra. The effect of the loading amount of h-BN and the ball milling time on the photocatalytic degradation of Rhodamine B (RhB) and methylene blue (MB) was investigated. The results indicated that the photocatalytic activity of TiO2 could be improved substantially by coupling with a proper amount of milled h-BN. The optimal loading amount of h-BN was found to be 0.5 wt% and the milling time was 30 min. Under this condition, the photocatalytic removal efficiencies of TiO2 for RhB and MB could be increased as high as 15 and 8 times. The role of the milling process and the mechanism for the enhancements was finally discussed in terms of creation of negatively charged h-BN surface and promotion the separation of photoinduced holes, respectively. (C) 2012 Elsevier B.V. All rights reserved.