A facile hydrothermal route assisted by polyethylene glycol (PEG) 400 was utilized to synthesize single-phase Bi2Fe4O9 crystallites. X-ray diffraction results showed the products with PEG 400 of 30 g/L exhibited a preferred growth along the (001) plane. Transmission electron microscopy indicated that the morphology of the as-prepared Bi2Fe4O9 crystallites with PEG 400 were plake-like and rod-like. Strong absorption in visible-light region of the products was characterized by UV-vis diffuse reflectance spectrum (UV-DRS). The photocatalytic activity of Bi2Fe4O9 crystallites was evaluated on degradation of methyl orange (MO) under visible light irradiation. For 3 h irradiation, the degradation ratio was increased to 93% with the aid of a small amount of H2O2. The analysis of FT-IR spectra proved that the Bi2Fe4O9 catalysts were remained stable after the photocalytic reactions.