Nanocrystalline Al2O3 powder has been successfully synthesized by a simple and fast sol-gel auto-combustion method. The transformation of crystalline phases of as-synthesized nano powders was investigated through X-ray diffraction in terms of their crystallinity and crystallite size. Subsequently, a detailed transmission electron microscopy (TEM) investigation, including specific area electron diffraction (SAED) analysis revealed the crystallographic alterations and morphological information even at lattice scale which co-include the XRD analysis. The results obtained allow to explain the evolution of an amorphous state into different crystalline phases with increased calcining temperature; and their relation to particle size. The particle size is found to be closely related to phase transition of Al2O3 from γ � δ � θ � κ � α. The existence of distinctive bonds and band energy were studied by employing Fourier-transform infrared spectroscopy (FTIR) and UV-visible spectroscopy, respectively. On the other hand, thermo gravimetric analysis (TGA) had also been performed to confirm the phase purity of nano powder. © 2016 Trans Tech Publications, Switzerland.