Mesoporous Fe3O4 nanoparticles coated with ZnO nanocrystals were successfully synthesized by a simple solution method at low temperature. The transmission electron microscopy analysis indicates that the mesoporous Fe3O4 nanoparticles are monodispersed with a mean diameter of 160 nm and the thickness of ZnO layer is 15 nm approximately. The porosity of the products was further substantiated by the nitrogen (N2) sorption measurement. The N2 adsorption-desorption isotherm curve can be identified as type IV, which is a characteristic of mesopores. Electromagnetic (EM) wave absorption properties of the as-prepared Fe3O4@ZnO mesoporous spheres-wax composites were investigated at a room temperature in the frequency range of 0.5∼18 GHz. Interestingly, the Fe3O4@ZnO mesoporous spheres exhibit an enhanced EM wave absorption due to the mesoporous structure. The multiple absorbing mechanisms result from the interface polarization induced by the special core/shell and mesoporous structures as well as dipole polarization of both Fe3O4 and ZnO. The results demonstrate that the Fe3O4@ZnO mesoporous spheres are attractive candidates for a new kind of EM wave absorption materials with wide absorption frequency band.