As a direct band gap photocatalyst, BiOF has attracted considerable attention in photocatalytic field due to its unique layered structures. However, it is highly challenging to prepare BiOF with excellent photocatalytic performance. In this paper, a facile and efficient PVA-assisted hydrothermal preparation of BiOF was reported. The samples were characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), Brunauer-Emmett-Teller method (BET), surface photovoltage (SPV) spectroscopy and particle size analyzer. The photocatalytic activity of PVA-BiOFwas evaluated by decolorization of methyl orange (MO) aqueous solution. The results reveal that photocatalytic activity of PVA-BiOF is ten times of that of the reference BiOF. The enhancement photocatalytic performance of PVA-BiOF can be attributed to the enhanced surface area and the accelerated formation of O2−.