The effect of Sn for Ti substitution on the crystal structure of a perovskite, barium titanate stannate (BTS), BaTi_1−xSn_xO₃forx= 0, 0.025, 0.05, 0.07, 0.10, 0.12, 0.15 and 0.20, was investigated. The powders were prepared by the conventional solid-state reaction technique. The structural investigations of the BTS powders were done at room temperature by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), selected-area electron diffraction (SAED) and Raman spectroscopy analyses. Rietveld refinement of XRD data indicates that gradual replacement of titanium by tin in BaTiO₃provokes a phase transition from tetragonal for 0 ≤x≤ 0.07 to cubic forx= 0.12, 0.15 and 0.20. The coexistence of tetragonal (P4mm) and cubic (Pm\overline 3m) crystal phases was established in powder with nominal composition BaTi_0.9Sn_0.1O₃. The crystal phases determined by Rietveld refinement were confirmed by HRTEM and SAED analyses. The crystal structures of the BTS powders at short-range scale were studied by Raman spectroscopy, which shows tetragonal (P4mm) and a small fraction of orthorhombic (Pmm2) crystal phases for all the examined BTS powders, implying a lower local ordering when compared to the average symmetry.