A peroxopolyoxotungsten-based ionic hybrid was synthesized by anion-change of peroxopolyoxometalate (POM) $PW_4O{_{24}}^{3-}$ with dicationic long-chain alkyl imidazolium ionic liquids. The characterization was conducted by FT-IR, TGA, $^1H$-NMR and CHN Elemental analyses. Its catalytic performance was evaluated by the epoxidation of soybean oil with $H_2O_2$ under solvent-free condition, including testing of organic cations influence, catalytic reusability and reaction conditions. The catalyst was proved to be a highly efficient recyclable catalyst for epoxidation of various vegetable oils with $H_2O_2$, showing high $H_2O_2$ utilization efficiency, high catalytic activity, convenient recovery and good reuse ability.