In this study, a magnetically-recoverable catalyst (Fe₃O₄@SiO₂-HPW) was prepared by the application of phosphotungstic acid (HPW) supported on silica-coated Fe₃O₄ nanoparticles. The prepared samples were characterized by XRD, TEM, FT-IR, and N₂-adsorption–desorption isotherms. The content of W in Fe₃O₄@SiO₂-HPW was measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and its surface acidity was determined by a potentiometric titration with n-butylamine. Fe₃O₄@SiO₂-HPW showed an excellent catalytic activity for the synthesis of EMF from HMF and fructose. Under optimal reaction conditions, EMF was obtained in a high yield of 83.6% by the etherification of 5-hydroxymethylfurfural. EMF could also be synthesized directly from fructose in a yield of 54.8% via a one-pot reaction strategy. After reaction, the catalyst Fe₃O₄@SiO₂-HPW could be easily separated from the reaction mixture with an external magnetic field, and it could be reused at least five times without any loss of its catalytic activity.