Abstract: A series Fe-modified mesoporous SiO₂ (Fe-SiO₂) composites were successfully synthesized via one-step method. Fe species can be co-precipitated with the siliceous species in the mildly acidic aqueous solutions that contain the template and aluminum chloride. The structure, morphology and chemical composition of Fe-SiO₂ composites were characterized by XRD, N₂ physisorption, FTIR, UV-vis, SEM and EDS techniques. The obtained mesoporous Fe-SiO₂ composites was then used to adsorb and synergetic catalytic degrade organic methylene blue (MB) from wastewater. The effects of the initial Fe content in the reaction solution on the structure and property of Fe-SiO₂ composites were thoroughly investigated. The results show that the mesoporous Fe-SiO₂ synthesized with relatively low Fe content (rFe:Si ≤ 0.05) has a well-ordered mesostructure and large surface area (860-889 m²·g^-1), and Fe species are highly dispersed in the framework of the SiO₂. At high Fe content (rFe:Si=0.1), the obtained mesoporous Fe-SiO₂ has a reduced surface areas of 526 m²·g^-1, and Fe species are existing in the matrix of SiO₂ as the both framework and extra-framework forms. All of the mesoporous Fe-SiO₂ composites show high adsorption capacities and the superior heterogeneous Fenton-like catalytic activities for the removal of MB from aqueous solutions. Among them, the Fe-SiO₂ sample synthesized with the rFe:Si of 0.05 presents the best performance. It can remove 213 mgg^-1 of high concentrated MB (250 mg·L^-1) by adsorption and synergetic catalytic degradation.