In the present work we investigated the interactions established between red mud (RM) and phosphate anions (P) at pH 4.0, 7.0 and 10.0. The amount of P sorbed by RM (P-RM) increased as the pH decreased being equal to 4.871 mmol•g-1 at pH 4.0, 0.924 mmol•g-1 at pH 7.0, and 0.266 mmol•g-1 at pH 10.0. Sequential extractions’ data of P-RM equilibrated at pH 4.0 and 7.0, suggested that the phosphate sorption at these pH values was mainly regulated by two different mechanisms that gave rise to a chemical adsorption on RM phases, and to the formation of metal phosphate precipitates. By contrast, at pH 10.0 the P-sorption was regulated by a chemisorption mechanism on Fe-Al phases of RM. These findings were supported by FT-IR analysis, which showed a broad band at 1114 and 1105 cm−1 in P-RM spectra at pH 4.0 and 7.0 respectively, attributable to P-O(H) stretching ν3-modes associated to inner-sphere complexes of phosphate on Fe-Al phases, or alternatively to stretching vibrations of PO43- tetrahedra, arising from a precipitate of aluminium-phosphate. Importantly, the FT-IR spectroscopy showed a phosphate-promoted dissolution of tectosilicates, notably cancrinite and sodalite, in RM exchanged with phosphate at pH 4.0 and 7.0.