Blue photoluminescent emission was observed in pure nanometer-sized γ–Al2O3 powders prepared by the sol-gel process, with aluminum alkoxide as the precursor. The photoluminescent excitation spectrum detected at »em = 422 nm showed four peaks located at 238, 255, 278.5, and 348.5 nm, respectively, the first having the strongest intensity. The photoluminescent emission spectra were made up of a broad band with four peaks located at 404.5, 422, 447, and 484.5 nm. The emission band of 422 nm had the intensity. We suggest that the defect level in the nanometer alumina powder also is the main reason for the appearance of new luminescent emission bands.