Abstract：The magnetic microspheres with polystyrene (PS) spheres as cores and Mn-Fe oxide as shells were synthesized by deposition and surface reaction. The effect of different ratios of manganese salt on magnetic product was studied. To obtain the hollow magnetic microspheres, the PS core in spheres was removed by calcination and extraction in solvent, respectively. The relation of calcination temperature to the spheres specific surface area was investigated. The removal efficiency of PS via extraction was also examined. In comparison of the calcination and extraction in solvent, it is shown that the hollow Mn-Fe oxide microspheres obtained from the former way are better than those from the latter one. The optimal conditions to form hollow Mn-Fe oxide microspheres by calcination were explored, the results show that the saturation magnetization and specific surface area of the hollow Mn-Fe oxide microspheres were measured as 68.66 emu/g and 27.8438 m2/g respectively when calcinated at 400℃.