A novel heterogeneous Fenton photocatalyst was prepared by supporting Fe(bpy)(3)(2+) onto amidoximated polyacrylonitrile (PAN) fiber and then used for the degradation of organic dye under visible irradiation. FTIR, XPS and UV-vis diffuse reflectance spectroscopy analyses suggest that the Fe(bpy)(3)(2+) molecules were distorted during their immobilization onto the fiber support, and the O-H groups in amidoxime group had interacted with Fe(bpy)(3)(2+). Upon visible light irradiation, the catalyst was found to be highly effective for the degradation and mineralization of Rhodamine B at a neutral pH and could be easily recycled without any loss of activity. The interaction of O-H groups with Fe(bpy)(3)(2+) groups was considered to be responsible for the high catalytic performance since the Fe(bpy)(3)(2+) supported on unmodified PAN fiber did not show any photoactivity. The O-H groups in conjunction with 2,2'-bipyridine ligands may provide a flexible bifunctional coordination environment for iron (II/III) ions. ESR studies indicate that hydroxyl radicals are involved in this photocatalysis process, and a possible mechanism is proposed. (C) 2013 Elsevier B.V. All rights reserved.