The crystallization kinetics in BaTiO3 synthesis from hydrate precursors via microwave-assisted heating (MWH) were investigated. The structural and chemical features of powders synthesized via MWH and conventional heating (CH) were compared. The charged radicals generated under microwave irradiation were identified by chemical analysis and real-time charge flux measurements. Using Ba(OH)2∙H2O (BH1), Ba(OH)2 (BH0), and BaCO3 (BC) as the precursors for a Ba source, and TiO2∙4H2O (TH) for a Ti source, three different mixture samples, BH1TH (BH1 + TH), BH0TH (BH0 + TH), and BCTH (BC + TH), were heat-treated in the temperature range of 100–900 °C. BaTiO3 powders were synthesized at temperatures as low as 100 °C when sample BH1TH was subjected to MWH. Based on the growth exponent (n), the synthesis reactions were inferred to be diffusion-controlled processes (3 ≤ n ≤ 4) for MWH and interface-controlled processes (2 ≤ n ≤ 3) for CH. Current densities of approximately 0.073 and 0.022 mA/m2 were measured for samples BH1TH and BH0TH, respectively, indicating the generation of charged radicals by the interaction between the precursors and injected microwaves. The radicals were determined as OH− groups by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy.