BaTiO₃ and BaSnO₃ samples doped with Eu³⁺ ions were prepared using glycine-nitrate gel combustion method. Relative intensities and line shapes of magnetic dipole allowed ⁵D₀ → ⁷F₁ and electric dipole allowed ⁵D₀ → ⁷F₂ transitions of Eu³⁺ from the hosts, BaTiO₃ and BaSnO₃, are significantly different. Based on detailed structural investigations, it is confirmed that synthesized BaTiO₃ sample is tetragonal with no center of symmetry around Ba²⁺ ions. Unlike this BaSnO₃ is cubic with centrosymmetric Ba²⁺ site. From X-ray diffraction and experimentally obtained Judd–Ofelt parameters (Ω₂ and Ω₄ values), it is confirmed that in BaTiO₃ there is a decrease in the average Ba–O and Ba–Ba distances compared with that in BaSnO₃. This leads to higher Eu–O bond polarizability and adds to the distortion in its environment around Eu³⁺ in BaTiO₃:Eu compared with BaSnO₃:Eu. This is responsible for the observed difference in the luminescence properties.