The H3 xPMo12-xVxO40(x=1-3) with keggin structure was prepared by Na2HPO4, NaVO3 Na2MoO4?2H2O according to the stoichiometric coefficient. Then the [Bmim]3 xPMo12-xVxO40(x=0-3) hybrid materials was prepared by the H3 xPMo12-xVxO40(x=0-3）and the 1-utyl-3-methyl imidazole bromide ionic liquid. The IR spectra and XRD characterization showed the synthetic [Bmim]3 xPMo12-xVxO40(x=0-3) hybrid materials have keggin structure. The SiO2-supported [Bmim]3 xPMo12-xVxO40(x=0-3) hybrid materials were obtained. And the prepared samples were apply to the research of the degradation of organic dye methyl orange. The optimal reaction conditions were determined: when [Bmim]5PMo10V2O40/SiO2 loading was 50 wt.%, the temperature of reaction was 50 oC, the dosage of hydrogen peroxide was 5 mL, the catalyst was 0.5 g, the highest rate of degradation of organic dye Methyl orange reached up to 94 %. The catalyst has good regeneration performance, which can be reused at least four times. The degradation rate of Methyl orange has no significant decline.