The distribution of sorbed arsenic(V) among different geochemical fractions for arsenic(V)-loaded red mud, an oxide-rich residue from bauxite refining that has been proposed as an adsorbent for arsenic, was studied as a function of sorbed arsenic(V) concentration using a sequential extraction procedure. The release of previously sorbed arsenic(V) was also studied as a function of pH and arsenic(V) concentration. Most sorbed arsenic(V) (0.39–7.86 mmol kg−1) was associated with amorphous and crystalline Al and Fe oxides (24.1–43.8% and 24.7–59.0% of total sorbed arsenic, respectively). Exchangeable arsenic was the smallest fraction (0.4–5.2% of total sorbed arsenic). The distribution of sorbed arsenic(V) was related to the arsenic surface coverage. For arsenic surface coverages >~30% the percentage of arsenic(V) associated with the amorphous Al oxide fraction increased and that associated with the crystalline oxide fraction decreased. The arsenic(V) exchangeable fraction increased from 1.4 to 756 μmol kg−1 as surface coverage increased from 388 to 7855 μmol kg−1. The release of sorbed arsenic(V) from red mud was greater at alkaline pH values (maximum release of ~33% of previously sorbed arsenic at pH = 12), but for high arsenic(V) initial concentration (0.2 mM arsenic) considerable amounts of arsenic (6.5% of previously sorbed arsenic) were released at pH 4, in accordance with the dissolution of amorphous Al oxides in the red mud. The results obtained suggest a greater mobility of sorbed arsenic(V) as its surface concentration approaches saturation.