A facile hydrothermal synthetic method was employed for the preparation of Fe 3+ coordinated to amino-functionalized spherical mesoporous silica (Fe–NH 2 –SMS), aimed at the rapid and efficient removal of As(V) from water. The morphology, structure and properties of the adsorbent were characterized via SEM, EDS, N 2 adsorption–desorption, FT-IR, zeta-potential and XPS. Fe–NH 2 –SMS exhibited a high performance for As(V) removal with a very fast adsorption rate (reaching equilibrium within 1 min). As(V) adsorption on Fe–NH 2 –SMS was better fitted to the Langmuir isotherm model ( R 2 = 0 .988). The maximum adsorption capacity was 43.34 mg g –1 As(V) at 25 °C. The optimum pH for As(V) adsorption was in the range of 5–10. The individual presence of SO 4 2– , SO 3 2– , HPO 4 2– and CO 3 2– had a negative effect on As(V) adsorption. The removal of As(V) via Fe–NH 2 –SMS in real water samples remained above 95% with an increasing adsorbent dosage up to 1.6 g L –1 . Reusability studies indicated that the removal of As(V) was still up to 76% after five adsorption–desorption cycles. Electrostatic attraction and inner-sphere complexation between As(V) and functional groups (–NH 2 ⋅ ⋅ ⋅ Fe 3+ ) were identified as the adsorption mechanisms of As(V). The prepared adsorbent can be considered a promising adsorbent for the rapid adsorption of As(V) from water. • Fe–NH 2 –SMS can reach the adsorption equilibrium within 1 min of contact time. • Fe–NH 2 –SMS showed wide pH applicability (5–10). • Fe–NH 2 –SMS exhibited the excellent As(V) removal of 99%. • As(V) removal of real water samples was satisfactory. • As(V) adsorption mechanism was electrostatic attraction and inner-sphere complexation.