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Tetragonal barium titanate (BaTiO3) was synthesized via sol-gel method and calcined at 900 °C. The crystal phase of barium titanate still remained after doping with sodium showing that the phase had not been distorted by dopants. However, an additional phase of sodium barium titanium oxide (Na1.7Ba0.45Ti5.85O13) was detected and is believed to be formed on the surface of particles. Surface microstructures of undoped BaTiO3 show no distinct shape and high agglomeration. These preparations described the effects of different calcination duration on the composition and shape and size of BaTiO3 particles. Upon doping with sodium, the morphology of the particles becomes distinct. However, with the effect of increasing calcination duration from 2 to 6 hours, the morphology of particles progressively transformed from cube to sphere. Particles agglomeration was still unavoidable. The average size of the particles varied slightly between 0.24 - 0.36 μm with narrow size distribution after calcination. [ABSTRACT FROM AUTHOR]