In the present work, we have discussed the structural and photoluminescent properties of Al2O3 nanoparticles doped with Cr3+ ion prepared through solution combustion synthesis (SCS) technique. SCS is a well-known method for the production of different metal oxides and composite materials such as metal matrix composites and for producing this need an extra reduction step. The set of samples differing in activator concentration were studied carefully by means of structural and optical characterization methods. In particular, the transmission electron microscopy (TEM) has been deployed together with X-ray diffraction (XRD) technique to determine fundamental structural properties of nanoparticles. XRD results showed that pure alpha-Al2O3 single phase was obtained and TEM result indicates that nanoparticles are spherical in shape. The selected area electron diffraction (SAED) and Energy dispersive analysis by X-rays (EDAX) analysis suggested the crystallinity and chemical composition of the Cr3+ doped Al2O3. The change in crystal structure parameters was obtained by Rietveld refinement method. The optical characterization focused mainly on the basic excitation and emission features and their sensitivity to the dopant concentrations. The excitation spectrum of Cr3+-doped Al2O3 nanopowders consist of two bands peaking at 406 nm and 570 nm and the emission spectrum consist of two bands peaking at 694 nm and 670 nm. (C) 2013 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.