The interaction of Eu3+ with Sb3+ ions during the room temperature synthesis of luminescent Sb2O3 nanorods is investigated using luminescence and vibrational spectroscopic techniques. Our results demonstrate that well crystalline, oriented Sb2O3 nanorods having length of around 3–4μm, a width of around 100–200nm and luminescence at around 390nm can be synthesized at room temperature. Incorporation of Eu3+ in these nanorods has been attempted and it is found that Eu3+ ions do not have any interaction with nanorods 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.