Two transition metal ions (Fe3+ and Cu2+) and a rare earth metal ion (Ce3+) were selected to coordinate with amidoximated polyacrylonitrile (PAN) nanofibrous membrane for preparing three metal modified PAN nanofibrous membrane complexes (M‐AO‐n‐PANs, M = Fe, Cu, or Ce) as the heterogeneous Fenton catalysts for the dye degradation in water under visible irradiation. The coordination kinetics of three metal ions with modified PAN nanofibrous membranes was studied and the catalytic properties of the resulting complexes were also compared. The results indicated that increasing metal ion concentrations in solution or higher coordination temperature led to a significant increase in metal content, particularly in Fe and Cu contents of the complexes. Their coordination process could be described using Langmuir isotherm and pseudo‐second‐order kinetic equations. Moreover, Fe‐AO‐n‐PAN had the best photocatalytic efficiency for the dye degradation in acidic medium, but a lower photocatalytic activity than Cu‐AO‐n‐PAN in alkali medium.