Copper-containing hexagonal mesoporous silicas (Cu-HMS) with different Si/Cu atomic ratios were synthesized by one-pot sol-gel method using dodecylamine surfactant as templating agent. The Structure was characterized by X-ray diffraction, N-2 adsorption-desorption, infrared spectroscopy, transmission electron microscopy, ultraviolet and visible diffuse reflectance spectroscopy, electron spin resonance and H-2 temperature-programmed reduction. The results show that the Cu-HMS material is an efficient catalyst for epoxidation of styrene with use of aqueous tert-butylhydroperoxide. The catalytic performance is dependent on Si/Cu atomic ratio and reaction solvent. A styrene conversion of 99% with epoxide selectivity up to 84% can be obtained over the Cu-HMS material with Si/Cu atomic ratio of 40 in the case of using a mixed solvent of acetonitrile and N,N-dimethylformamide. No significant loss in the catalytic performance is observed during catalyst reuse. The enhanced catalytic performance over Cu-HMS material may be attributed to the homogeneous dispersion and uniformity of active Cu2+ species. (C) 2009 Elsevier B.V. All rights reserved.