Fe3O4 hollow microspheres with good dispersibility and high saturation magnetization were synthesized through a facile one-step solvothermal method. The formation mechanism of the hollow structure was studied by taking time-dependent experiments. Porous [Formula: see text]-FeOOH and [Formula: see text]-Fe2O3 nanosheets were firstly fabricated. Fe3O4 solid spheres aggregated by small particles were obtained from the transition of [Formula: see text]-FeOOH and [Formula: see text]-Fe2O3. Finally, the solid sphere is transferred to hollow sphere through Ostwald ripening. The maximum saturation magnetization of the hollow spheres is [Formula: see text][Formula: see text]emu/g, which is higher than some results reported in references. The Fe3O4 hollow spheres show potential applications in microwave absorption and photocatalysis.