In this work, barium titanate (BaTiO₃) powders were synthesized via two Pechini sol-gel processes using citric acid and polyethylene glycol-6000 as chelating agents. Attempts had been made to understand the thermal behavior of the polymeric intermediates with the help of thermogravimetry-differential scanning calorimetry (TG-DTG-DSC) thermograms. The structural coordination of as-prepared polymeric intermediates was investigated by Fourier transform infrared (FTIR) analysis. The phase and structure of the powders calcined at different temperatures were characterized by X-ray diffraction (XRD) and field emission scanning electron microscope (FE-SEM). Preparation of the polymeric precursors can influence the mechanism of the BaTiO₃ synthesis. The formed intermediate phase BaCO₃ appears in gel-2 system, and BaCO₃ phase does not disappear at 720°C. The formed intermediate phases of gel-1 differ from that of gel-2. The intermediate phases of gel-1 are anatase TiO₂ and rutile TiO₂, and the intermediate phase BaCO₃ doesn't appear in gel-1system. When the powders are calcined at 720°C, the particles of gel-1 system are agglomerated spheres with about 25 nm, but the particles of gel-2 system have varied shapes.