Carbon-supported gold catalysts Au/C were prepared by an impregnation-reduction method and modified by AgNO3 to obtain bi-metallic catalysts Au-Ag/C, which were characterized by X-ray-diffraction (XRD) and Transmission Electron Microscope (TEM). Their catalytic performance was tested in the oxidation of cyclohexene in an autoclave without any solvent. The results showed that Ag doping can significantly enhance the catalytic performance of carbon-supported gold catalyst. Au(1.0 wt.%)-Ag(1.0 wt.%)/C has been found to be an efficient catalyst for the cyclohexene oxidation with a conversion of 27.6% at 80 °C and 0.4 MPa for 12 h while selectivity for ∑C6 products (including cyclohexene oxide, 2-cyclohexene-1-ol, 2-cyclohexene-1-one and cyclohexane-1,2-diol) exceeding 88.9%, especially the selectivity of cyclohexane-1,2-diol up to 47.6%. Moreover, the effects of Au, Ag content on catalytic performance were also reported.