The interaction of Eu³⁺ with Sb³⁺ ions during the room temperature synthesis of luminescent Sb₂O₃ nano rods  is investigated using luminescence and vibrational spectro scopic techniques.Our results demonstrate that well crystalline, oriented Sb₂O₃ nano rods having length of around 3–4 mm, a width of around 100–200nm and luminescence at around 390nm can be synthesized at room temperature. Incorporation of Eu³⁺ in these nano rods has been attempted and it is found that Eu³⁺ ions do not have any interaction with nano rods and their orientation. Detailed Eu³⁺ luminescence and XRD studies confirmed that a part of Sb³⁺ ions reacts with Eu³⁺ ions in the presence of hydroxyl ions (present in the medium)to form an amorphous antimony europium hydroxide compound. The amorphous compound on heating at high temperatures leads to its decomposition, giving hydrated Sb(V) oxides and Eu₂O₃ as major phases.