Magnesium oxide hollow spheres without a template core were conveniently prepared by stabilized bubble formation in a hybrid solution containing a magnesium acetate precursor, thus avoiding the complicated preparation process using a template. The hollow sphere could be aligned along the radial striation by spin coating, and its diameter from a micrometer to submicrometer dimension could be easily modified by the solution composition. It was also possible to control the open or closed hollow sphere by changing the solvent. Thus, the produced magnesium oxide hollow sphere is envisioned to have applications in many areas such as medicine, analysis, optics, and so on.