Abstract: Vanadium-phosphorous oxide catalysts modified with bismuth were prepared by coprecipitation and characterized by X-ray diffraction（XRD），FTIR and SEM. Catalytic behavior of the prepared Bi-modified vanadium-phosphorous oxide catalysts for selective oxidation of cyclohexane with hydrogen peroxide as the oxidant was investigated with variations in Bi/V and P/V molar ratios，solvent and temperature. Results showed that cyclohexane conversion and selectivity for cyclohexanone were obviously improved with the increase in Bi/V molar ratio. The P/V molar ratio showed a great influence on catalyst structure and performance. The addition of P could significantely destroy the crystal structure of V2O5 by producing some phosphates. Under optimized conditions，n（Bi）/ n（V）=0.1，n（P）/ n（V）=0.92，acetone as the solvent at 65 ℃for 8 h， cyclohexane conversion，cyclohexanone and cyclohexanol yields were 81.4%，58.2% and 23.2%，respectively.