<p>Carbonate, oxide, and nitrate precursors were mixed in a citric acid-ethylene glycol solution and then subjected to solid-state reaction in order to prepare Pr-doped SrBi₂Nb₂O₉ compounds. X-ray diffraction (XRD) measurements confirmed that all prepared samples had orthorhombic symmetry belonging to the SrBi₂Nb₂O₉ structure. The unit cell volume tended to decrease when Pr was incorporated into the lattice structure. The NbO₆ octahedron vibration was revealed by Fourier transform infrared (FTIR) spectroscopy, and the presence of the praseodymium ion within the structure was confirmed by photoluminescence measurements. Meanwhile, the dopant-dependent direct bandgap was revealed by ultraviolet–visible (UV–Vis) diffuse reflectance. The Curie temperature did not change with frequency, indicating that all of the ceramics were normal ferroelectrics. The results indicate that the ferroelectric transition temperature was affected by the occupied site rather than valence, and thus there was no linear correlation between the amount of Pr³⁺ ion doping and the ferroelectric transition temperature. Therefore, either the Bi-site or the Sr-site was randomly substituted. As for room-temperature effects, Pr³⁺ ion doping did not improve the dielectric loss. At high temperatures, the conduction mechanism arose from doubly ionized oxygen vacancies and the hopping process.</p>