The modified Pechini method using ethylenediaminetetraacetic acid as a chelating agent to prepare Ba2Ti9O20 is reported. The resin precursors were prepared and heated at 700 to 1200 °C in air, and x-ray diffraction was used to determine the phase transformations as a function of temperature. Single-phase Ba2Ti9O20 was obtained at 1200 °C for 2–6 h, without the need of prolonged heat treatment time. The process was simple and easy to control: low-temperature conditions or a protective atmosphere was not needed. Differential thermal analysis, thermogravimetric analysis, and Raman spectroscopy were used to characterize the precursors and derived oxide powders. Details of the synthesis and characterization of the resultant products were given.