In the present work, pure BiFeO 3 and pure Bi 2 Fe 4 O 9 single phases were successfully synthesized by tailoring hydrothermal synthesis route. The structural and morphology analyses have been achieved by X-ray diffraction and by electron microscopy. Scanning and transmission electron microscopy images revealed a strong change in the morphology from agglomerated nanoparticles with sizes less than 10 nm for BiFeO 3 to plate-like particles with larger sizes (edges of 100 to 200 nm while a thickness of * 30 nm) for Bi 2 Fe 4 O 9 . Such a small size obtained for BFO nanoparticles has never been observed before for similar synthesis method without any added reagents, to the best of our knowledge. The photocatalytic activity of the as-prepared samples for degradation of methylene blue dye under sunlight irradiation shows a good efficiency. It reaches 61% and 83% after 3 h for BiFeO 3 and Bi 2 Fe 4 O 9 nanostructures, respectively. Despite a bigger size and higher bandgap, the better efficiency of Bi 2 Fe 4 O 9 compared to BiFeO 3 is explained by a much stronger absorption especially for light with energy higher than 2.65 eV.