Many efforts have been devoted to exploring novel luminescent materials that do not contain expensive or toxic elements, or do not need mercury vapor plasma as the excitation source. In this paper, amorphous Al2O3 powder samples were prepared via the Pechini-type sol-gel process. The resulting samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), photoluminescence (PL) excitation and emission spectra, kinetic decay, and electron paramagnetic resonance (EPR). The obtained amorphous Al2O3 powder samples annealed at 500 and 600 degrees C exhibit bright bluish-white emission centered at 430 and 407 nm, respectively. The luminescent mechanisms of the amorphous Al2O3 powder samples can be ascribed to the carbon-related impurities such as radical carbonyl species. The calculated band structure of the defective amorphous Al2O3 agrees well with the results of spectral analysis and the proposed luminescent mechanism.