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 photolumine- scence-band observed over the region of 500–600 nm is arising due to the morphology of Sb₂O₃ nanorods. Changes in the Raman spectrum at ~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.