A series of biopolymer based complex were manufactured by coordinating iron ions to the abundant amino- and sulfur-containing groups in the modified wool and used as heterogeneous Fenton-like photocatalyst for 4-chlorophenol(4-CP) degradation in the presence of H_2O_2.Hydroxylamine hydrochloride(NH_2OH·HC1) or acrylic acid was employed to modify the natural wool to strengthen the interaction with iron and to reinforce the structural stability.The NH_2OH·HC1 modified wool based complex showed the best catalytic performance for 4-CP degradation.The strong coordination between iron and great number of hydroxamic acid in this modified complex leads to the least iron leaching during the tests.HO· species was confirmed to be the dominant reactive oxidant in the decontamination process.The approach presented in this study can provide a new approach for developing novel bioployermer-based photocatalysts for efficient degradation of toxic organic pollutants such as 4-CP. A series of biopolymer based complexes were manufactured by coordinating iron ions to the abundant amino- and sulfur-containing groups in the modified wool and used as heterogeneous Fenton-like photocatalyst for 4-chlorophenol (4-CP) degradation in the presence of H 2 O 2. Hydroxylamine hydrochloride (NH 2 OH · HCl) or acrylic acid was employed to modify the natural wool to strengthen the interaction with iron and to reinforce the structural stability. NH 2 OH · HC 1 modified wool based complex showed the best catalytic performance for 4-CP degradation. strong coordination between iron and great number of hydroxamic acid in this modified complex leads to the least iron leaching during the tests. HO · species was confirmed to be the dominant reactive oxidant in the decontamination process. The approach presented in this study can provide a new approach for developing novel bioployermer-based photocatalysts for efficient degradation of toxic organic pollutants such as 4-CP.