Due to intake of excessive fluoride in drinking water, endemic fluorosis, the most widely distributed endemic diseases has caused worldwide attention. In this study, akaganeite anchored graphene oxide (β-FeOOH@GO) nanocomposites were synthesized by in situ forced hydrolysis of ferric chloride in presence of graphene oxide under facile condition. β-FeOOH@GO was characterized and evaluated as a new potential carbon sorbent for defluoridation in environmental application. The application pH, adsorption capacity, adsorption kinetic and anti-interference ability in defluoridation with β-FeOOH@GO was described. On the basis of Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) analysis, defluoridation mechanism involving the ion-exchange with chloride anions bearing in β-FeOOH@GO is indicated at molecular level from a new perspective way. It is a good supplement to classical hydroxyl replacement mechanism. It would be useful for the improvement of adsorption capacity and kinetics through designing facile anions-exchange adsorbents.