Consisted of closely packed nanoflakes, γ-Al2O3 hollow microspheres with ca. 4–6?μm in diameter, and 500–700?nm in shell thickness have been hydrothermally synthesized through utilizing Al(NO3)3·9H2O as precursor, urea as precipitant agent and sulfate K2SO4, (NH4)2SO4, or KAl(SO4)2·12H2O as additive, followed by a calcination step. The samples were further characterized by thermogravimetric analysis, scanning electron microscope, x-ray powder diffraction, nitrogen adsorption, and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of adsorbed CO etc. The morphology of alumina products was strongly dependent on the presence of SO4