In this work, lithium titanate oxide (Li4Ti5O12) (LTO) and praseodymium ion doped in lithium titanate oxide (Pr-LTO) were synthesized in a sol-gel simple method, and their catalytic effects on thermal decomposition of ammonium nitrate were reported using thermogravimetric analysis-differential scanning calorimetry (TGA-DSC) techniques. The X-ray powder diffraction, Brunauer-Emmett-Teller surface area measurements, particle size analysis, energy-dispersive X-ray spectroscopy, and scanning electron microscopy techniques were used to identify the structural properties and morphology of LTO and Pr-doped LTO. By doping the praseodymium ion within the LTO spinel structure, the surface area increases (from 204.2 m(2) g(-1) for LTO semiconductor to 318.9 m(2) g(-1) for Pr-doped LTO), and the catalytic activity improved. The catalytic effects of LTO and Pr-LTO on the thermal behavior of AN were studied via TG-DSC techniques. The thermal decomposition of pure AN (196-400 degrees C) shifted to lower temperatures, 154-280 degrees C, and 131-241 degrees C, in the presence of LTO and Pr-LTO, respectively. The results showed that the catalytic effects of LTO were improved by praseodymium doping. The Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Starink, and Tang methods were used to determine activation energies of all AN samples at different conversion values (alpha). The activation energies of pure AN values were 166 +/- 3, 166 +/- 2, 166 +/- 2, and 162 +/- 2 kJ mol(-1), while AN/LTO activation energies were 145 +/- 2, 144 +/- 1, 144 +/- 1, and 144 +/- 2 kJ mol(-1) and finally, those of AN/Pr-LTO were 112 +/- 1, 109 +/- 2, 110 +/- 1, and 110 +/- 1 kJ mol(-1) using FWO, KAS, Starink, and Tang methods, respectively.