Detailed luminescence studies on Eu³⁺ doped SrSnO₃ nano-rods having body centered tetragonal structure, confirmed that up to 1.5 at% Eu³⁺ ions occupy Sr²⁺ site in the lattice and is having a less polarisable environment. Experimentally obtained Judd–Ofelt parameters (Ω2 and Ω4 values) can be effectively used to monitor the extent of incorporation of Eu³⁺ ions at Sr²⁺ site. Based on Rietveld refinement of diffraction patterns and Sr K-edge EXAFS studies, it is inferred that average Sr–O and Sn–O bond lengths in SrO₁₂ and SnO₆ polyhedra increase with incorporation of relatively smaller Eu³⁺ at Sr²⁺ site in SrSnO₃ lattice.