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The metal oxide microspheres were successfully fabricated via an oil/water (O/W) emulsion process accompanied by sol-gel reaction.The core-shell structured hollow microspheres were obtained by heating the obtained gel microspheres at constant heating rate, while macroporous microspheres with incontinuous multicavities were fabricated by using polyvinylpyrrolidone (PVP) as the pore inducer in manufacturing process of the microspheres.The facile one-step route can be applied to synthesize titania, zirconia and alumina porous microspheres successfully.