Sodium bismuth titanate (Na0.5Bi0.5TiO3, abbreviated NBT) ceramics underwent concurrent successful synthesis on the basis of the hydrothermal method. A selected low-temperature process of thermal treatment was conducted to obtain a highly dense morphology, produced from high purity carbonates and oxides serving as initial precursors. The presence of well-crystallized NBT in the rhombohedral phase was also found at hydrothermal temperatures of 200°C. X-ray diffraction (DRX), Raman spectroscopy, Infrared spectroscopy (IR), and Scanning electron microscopy (SEM) analysis enabled to verify the structure, phase, morphology, and composition of the used samples. NBT ceramics exhibit features specific to relaxor ferroelectrics, with a diffusion exponent γ of up to 1.5 to promote their applications in micro-electromechanical and energy harvesting systems. The photocatalytic behaviors of NBT powders have been assessed by means of the degradation of methylene blue (MB) through UV-light irradiation. The samples prepared with precursors having a Na/Bi ratio of 0.5/0.5 showed the highest methylene blue (MB) photodegradation rate of 100% under UV irradiation for 420 minutes. In addition, photocatalytic activities under different masses and pH values were discussed for the first time. In addition, the photocatalyst has excellent stability, due to the larger particle size and surface area, which opens up new possibilities for the design of multi-component photocatalysts for future applications. The photocatalytic mechanism for the degradation of organic dyes (MB) has been principally assigned to the photoreduction process caused by superoxide radical anions (•O2−) and hydroxyl radicals (•OH).