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BaSnO grains with a rhombic dodecahedron shape have been synthesized via a facile modified hydrothermal approach. The structure and morphology evolution during hydrothermal treatment have been investigated with X-ray diffraction, scanning electron microscopy, and Raman and Fourier transform infrared spectroscopy. The sample with the single-phase of BaSnO can be obtained at the hydrothermal temperature of 24 °C, and the grain size grows with an increasing temperature from 10 to 15 μm below 270 °C. But the grain size decreases sharply to 4 μm when the temperature reaches 280 °C. The optical absorption and surface photovoltage spectroscopy analysis indicate that controlling the size and shape is of great importance in tuning photophysical properties of BaSnO powders. [ABSTRACT FROM AUTHOR]