Novel magnetic Bi2WO6/CeO2 hierarchical micro-spheres with grape-appearance morphology are effectively fabricated using a dependable and efficient method. The multi-functional compound microspheres are comprised of a magnetized core Fe3O4@SiO2, with an external shall layer of Bi2WO6/CeO2 heterostructure. The photoelectric performances of the samples are analyzed using photo-degradation of rhodamine B (RhB), surface photocurrent, and electrochemical impedance spectroscopy in visible light radioactivity. It is revealed that the Fe3O4@SiO2@Bi2WO6/CeO2 (FSBC) compound microsphere display greater performance of photocatalysis with the rate of reaction of 0.0721 min(-1), which is 1.44-fold and 38.3-fold stronger than that of the Fe3O4@SiO2@Bi2WO6 (FSB) composite and the CeO2 nanoparticle, correspondingly. Moreover, the FSBC composite micro spheres also display outstanding magnetic recoverability.