MoO 6 powders have been successfully fabricated via a sol-gel method starting from bismuth nitrate and ammonium molybdate. The as-synthesized samples were characterized by x-ray powder diffraction analysis, thermogravimetry and differential thermogravimetry, scanning electron microscopy, and ultraviolet-visible (UV-Vis) absorption spectroscopy. The results indicated the formation of a-Bi 2 Mo 3 O 12 and c-Bi 2 MoO 6 powders in acidic (pH 5) and alkaline (pH 9) conditions, respectively. a-Bi 2 Mo 3 O 12 exhibited irregular shape, while c-Bi 2 MoO 6 showed approximately flake-like morphology. The bandgap of pure a-Bi 2 Mo 3 O 12 and c-Bi 2 MoO 6 was estimated to be about 2.83 eV and 2.85 eV, respectively, according to UV-Vis studies. The slight shift of the absorption edge towards longer wavelength for a-Bi 2 Mo 3 O 12 indicated a decrease of the optical bandgap. Photocatalytic experiments showed that c-Bi 2 MoO 6 exhibited higher photodegradation activity of methylene blue compared with a-Bi 2 Mo 3 O 12 .