An innovative methodology was implemented for removing arsenic from aqueous solution by developing successive biosorption experiments. Considering the high affinity of As oxyanions toward Fe(III) oxides, the biosorption of Fe(II) was first conducted using nine biomaterials-aquatic and terrestrial invasive species, biowastes, local plants. Pistia stratiotes, an invasive alien species presenting the highest concentration of adsorbed Fe(II), was selected for a detailed investigation of As(V) removal from wastewater. After oxidation of the biosorbent into Fe(III), it yielded to a 92% removal efficiency determined by GFAAS and an excellent maximum biosorption capacity of 5.1 mg.g −1 . The biosorbent was characterized by MP-AES and HRTEM-EDX. The adsorption mechanisms for iron and arsenic have been studied via theoretical models and the Langmuir isotherms and pseudo-second-order kinetics models revealed excellent linearity and highlighted the robustness of the method. These promising results were developed to build a pilot for As(V) removal from the Russec river (Orbiel Valley, France), polluted with arsenic.