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Nanostructured hollow MgO microspheres were prepared by the template method. First, D-Anhydrous glucose was polymerized by the hydrothermal method to form a template. Second, a colorless solution was obtained by mixing magnesite with hydrochloric acid in a 1:2 proportion and heating in an 80 °C water bath for 2 h. Finally, the template from the first step was placed in the colorless solution, and the resulting precipitate was calcined at 550 °C for 2 h. The phase composition and microstructure of the calcined samples were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The XRD results indicated that the main crystal is periclase. The SEM results indicates that the template carbon microsphere surface is smooth, and the its size is uniform and concentrated in the range of 100⁻200 nm. The diameters of the samples range from 60 to 90 nm, which is smaller than the size of the carbon microsphere. The TEM results indicates that the sample is hollow with a shell thickness of about 6⁻10 nm. The specific surface area of the calcined hollow sphere is 59.5 m²·g^−1.