Magnetic Fe3O4-polydopamine (PDA) hybrid hollow microspheres, in which Fe3O4 nanoparticles were firmly incorporated in the cross-linked PDA shell, have been prepared through the formation of core/shell PS/Fe3O4-PDA composites based on template-induced covalent assembly method, followed by core removal in a tetrahydrofuran solution. The morphology, composition, thermal property and magnetic property of the magnetic hybrid hollow microspheres were characterized by SEM, TEM, FT-IR, XRD, TGA, and vibrating sample magnetometer, respectively. Results revealed that the magnetic hybrid hollow microspheres had about 380 nm of inner diameter and about 30 nm of shell thickness, and 13.6 emu g(-1) of magnetization saturation. More importantly, the Fe3O4-PDA hybrid hollow microspheres exhibited intrinsic peroxidase-like activity, as they could quickly catalyze the oxidation of typical substrates 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide. Compared with PDA/Fe3O4 composites where Fe3O4 nanoparticles were loaded on the surface of PDA microspheres, the stability of Fe3O4-PDA hybrid hollow microspheres was greatly improved. As-prepared magnetic hollow microspheres might open up a new application field in biodetection, biocatalysis, and environmental monitoring.