Mesoporous crystalline SiO2-Al2O3 was prepared by hydrothermal synthesis method and its supported Co or Mn catalysts were prepared by impregnation method. These prepared materials were characterized by XRD, XPS, NH3-TPD, BET, FT-IR and TG-DSC. It reveals that the metals are substituted into the framework as the form of MnCo2O4. Mn3O4, MnO, Co3O4 and stronger acid sites appear. Furthermore, Pyridine FT-IR spectra and NH3-TPD results indicate that both Bronsted and Lewis acid sites exist on these SiO2-Al2O3 supported transition metal catalysts and Mn/SiO2-Al2O3 exhibits higher Bronsted acid content. BET results show that SiO2-Al2O3 with middle Si/Al molar ratio has larger surface area and pore volume. The surface area and pore volume of SiO2-Al2O3 decrease after the introduction of the transition metals. The catalytic properties in the cyclohexane nitrosation to epsilon-caprolactam were performed and Mn/SiO2-Al2O3 exhibits better activity and selectivity to the epsilon-caprolactam. (C) 2011 Elsevier B.V. All rights reserved.