A series of Cu-Fe bimetal amidoximated polyacrylonitrile (PAN) fiber complexes with different molar ratios of Cu2+ to Fe3+ ions was prepared using a simple exhaustion method, and characterized using FTIR, DRS and XPS, respectively. Then they were tested as the heterogeneous Fenton catalysts for Rhodamine B degradation with H2O2 in the dark and under visible light irradiation. The results indicated that Cu-Fe bimetal amidoximated PAN fiber complexes could more effectively catalyze the dye degradation in water than Fe amidoximated PAN fiber complex, especially in the dark. And introduction of Cu2+ ions significantly increased their catalytic performance. 0.56 was the optimum molar ratio of Cu2+ to Fe3+ ions to achieve the best catalytic activity and stability. This was mainly due to the synergetic effect in the bimetal complexes. Visible light irradiation improved the catalytic activity of the complexes, especially with a low molar ratio of Cu2+ to Fe3+ ions. (C) 2011 Elsevier B.V. All rights reserved.