Nano particles of Eu³⁺ doped BaTiO₃ having a hexagonal structure, which is a thermodynamically stable phase above 1432ºC, have been prepared at a low temperature of 110ºC based on the coprecipitation of Ti^4+, Ba²⁺, and Eu³⁺ in ethylene glycol medium by adding urea. Based on differential thermal analysis studies, it is inferred that the as-prepared hexagonal phase of BaTiO₃:Eu³⁺ is unstable and decomposes to the anatase form of TiO₂ and barium carbonate above 420ºC. Luminescence properties of the hexagonal form of BaTiO₃:Eu³⁺ nanoparticles have been compared with cubic BaTiO3:Eu³⁺ nanoparticles prepared by the combustion method. Based on the detailed luminescence studies of Eu3⁺ in both cubic and hexagonal form of BaTiO₃ samples, it is inferred that Eu³⁺ ions mainly occupy the Ti⁴⁺ sites in hexagonal BaTiO₃ and both Ba²⁺ and Ti⁴⁺ sites in cubic BaTiO₃. A comparison of the luminescence properties of Eu³⁺ in hexagonal and cubic form of BaTiO₃ suggested that there is increased distortion around Eu³⁺ in hexagonal BaTiO₃ phase compared with cubic BaTiO3 phase, and this has been explained in terms of the distorted environment created around larger ionic radii Eu³⁺ ions occupying the smaller ionic radii Ti⁴⁺ site. There is a significant difference in the decay constant for ⁵D₀ level of Eu³⁺ for these two forms of BaTiO₃:Eu³⁺ nanoparticles.