Mn-ferrite composite hollow microspheres were prepared by a self-reactive quenching method. The effect of Zn adding on morphology, phase structure and electromagnetic parameters of the hollow microspheres were analyzed. The results show that most of the prepared powders are spherical hollow microspheres, and the particle size is in the micron range. A small amount of agglomerated particles fail to spheroidize but form irregular particles because the self-propagating reaction is not complete. The Mn0.5Zn0.5Fe2O4 ferrite composite hollow microspheres are obtained by adding metal Zn powders, and the properties of microwave electromagnetic loss are improved. The microwave absorption peaks move to higher frequency.