Magnetically separable catalysts were prepared and employed for the epoxidation of olefins with hydrogen peroxide. In all cases the magnetic core was firstly covered with a silica layer to prevent iron ion-initiated decomposition of hydrogen peroxide. The catalytic active species, an ionic liquid-type peroxotungstate, was then immobilized either by hydrogen bonding (catalyst 1) or by covalent SiO linkage (catalyst 2). In addition to a thorough characterization by FT-IR, XRD, NMR, DRIFT, XPS, and TEM, the catalytic potential was evaluated in the epoxidation of a variety of olefins as well as allylic alcohols. Both catalysts showed essentially a constant activity after at least ten consecutive cycles. On the basis of the research above, a new type of magnetically separable catalyst was constructed by immobilization of lacunary-type phosphotungstate by hydrogen bonding between the sulfonate anion and silanol group on the surface of the core–shell magnetic nanoparticles. After the detailed characterization, the catalyst was used in the epoxidation of a variety of olefins and allylic alcohols and was found to possess high activity, selectivity towards epoxides, and a constant activity after at least ten catalytic recycles without solvent.