Non-agglomerated nano-sized BaTiO3 powders were prepared by a 3 step decomposition of barium titanyl citric acid chelate derived from Ba(NO3)2-TiO(NO3)2-citric acid-NH4NO3 based complex compound system. The 1st step was the thermal treatment of chelate wet gel at 150°C for 40min to remove water and non-bridging hydroxyl groups and to form expanded gel intermediate. The 2nd step was the decomposition of the organic fuel by igniting expanded gel intermediate at 300°C. The 3rd step was the formation of the high purity BaTiO3 by calcining the decomposed powders at 700°C for 2 hours. The most expanded gel intermediate was found to be a decisive factor for the elimination of hard agglomerate. In addition, the initial oxidant/fuel molar ratio was shown to strongly influence the characteristics of the powders thus obtained. The optimum oxidant/fuel value was 3 for obtaining non-agglomerated pure BaTiO3 powders with a particle size of 50 nm. The agglomerate degree of BaTiO3 powders was determined by particle morphology and uniformity of the green compact microstructure observed by field emission scanning electron microscopy and scanning electron microscope.