Highly crystalline orthorhombic Sb2O3 nano-rods were prepared at room temperature by hydrolysis of SbCl3 in iso-propanol. Morphology induced changes in the photoluminescence properties of both the, as prepared as well as the annealed ones (at different temperatures) are presented. A distinct photoluminescence-band observed over the region of 500-600 nm is arising due to the morphology of Sb2O3 nanorods. Changes in the Raman spectrum at similar to 260 and 445 cm (1), corresponding to the Sb3+-O-Sb3+ stretching and bending modes, further confirm their shape selective nature. This study reveals significant effect of morphology on the structural and luminescent properties of Sb2O3. (C) 2009 Elsevier B. V. All rights reserved.