An amphiphilic composite with magnetic Fe3O4 core and dodecylamine-modified polyoxometalate-paired poly(ionic liquid) shell was synthesized and characterized by (1)H NMR, thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, UV-vis spectroscopy, X-ray diffraction (XRD), and digital microscopy. Catalytic tests for H2O2-based epoxidation of bioderived olefins, along with comparisons to various counterparts, demonstrate well that this newly designed catalyst exhibits high activity and selectivity, coupled with convenient magnetic recovery, and effective regeneration. The unique amphiphilic catalyst structure and the intramolecular charge transfer between amino groups and heteropolyanions are revealed to be responsible for the catalyst's excellent performances in epoxidation reactions.