In this paper, single-crystal magnetite hollow sub-microspheres with a narrow diameter distribution are synthesized through a simple solvothermal process in ethylene glycol in the presence of urea and a small amount of water. The determining role of water in the solvothermal synthesis is studied. It is found that a small amount of water is crucial for the formation of the magnetite hollow spheres. A novel formation mechanism of the magnetite hollow spheres is proposed based on the bubble-assisted Ostwald ripening. It is believed that the appropriate amount of CO 2 gas bubbles produced in situ by urea hydrolysis is crucial for the formation of hollow spheres. Because of the existence of gas microbubbles, magnetite solid spheres with a loose core and compact shell form, which is the key factor for the following inside-out Ostwald ripening and the formation of the hollow spheres. Thus, by simple changing of the water dosage, magnetite hollow spheres with different diameters and shell thicknesses are obtained controllably. The magnetic properties of the obtained magnetite hollow spheres are studied. It is found that the saturation magnetization of the magnetite hollow submicrospheres decreases with the increasing shell thickness, whereas the coercivity and remanent magnetization increase with increasing shell thickness.