Birnessite films on fluorine-doped tin oxide(FTO) coated glass were prepared by cathodic reduction of aqueous KMn O4. The deposited birnessite films were characterized with X-ray diffraction, Raman spectroscopy, scanning electron microscopy and atomic force microscopy.The photoelectrochemical activity of birnessite films was investigated and a remarkable photocurrent in response to visible light was observed in the presence of phenol, resulting from localized manganese d–d transitions. Based on this result, the photoelectrocatalytic oxidation of phenol was investigated. Compared with phenol degradation by the electrochemical oxidation process or photocatalysis separately, a synergetic photoelectrocatalytic degradation effect was observed in the presence of the birnessite film coated FTO electrode.Photoelectrocatalytic degradation ratios were influenced by film thickness and initial phenol concentrations. Phenol degradation with the thinnest birnessite film and initial phenol concentration of 10 mg/L showed the highest efficiency of 91.4% after 8 hr. Meanwhile, the kinetics of phenol removal was fit well by the pseudofirst-order kinetic model.? 2016 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences.Published by Elsevier B.V.