The adsorption of fluoride from aqueous solutions onto an Fe-impregnated chitosan (Fe-CTS) granular adsorbent was studied, and the adsorption capacity was determined to be 1.9736 mg g⁻¹ at an initial fluoride concentration of 10 mg L⁻¹. The effects of the initial fluoride concentration, dosage, and temperature were investigated using factorial design and analysis. The results indicated that high initial fluoride concentrations, low dosages, and low temperatures could enhance the fluoride adsorption capacity. In addition, Fe-CTS exhibited high selectivity for fluoride removal in the presence of high levels of several coexisting anions (nitrate, chloride, bicarbonate, and phosphate), except carbonate and sulfate. The adsorption process followed the Langmuir model at low fluoride concentrations and the Freundlich model at high initial fluoride concentrations. The data also fit the pseudo-second-order model. Scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, and extended X-ray absorption fine-structure (EXAFS) spectroscopy were used to elucidate the adsorption mechanism. The FTIR and EXAFS analyses revealed that Fe was chelated with –NH₂ and –OH groups on the CTS, and fluoride adsorption on the Fe-CTS occurred due to ion exchange between chloride and fluoride. Highlights: a granular Fe-impregnated chitosan (Fe-CTS) adsorbent was synthesized via chelation of Fe ions to –OH and –NH₂ groups of CTS. The Fe-CTS granular adsorbent exhibited high performance for the adsorption of fluoride. The mechanism of fluoride adsorption on Fe-CTS was elucidated using EXAFS and FTIR analyses. Fluoride adsorption on Fe-CTS occurred via ion exchange between chloride and fluoride.