Sorption behavior of As(V) by synthesized schwertmannite was examined under pH 3.3 as a function of As(V) concentration in the initial solution and interpreted in term of solid-solution reactions. Results showed that schwertmannite released 0.62 mmol of SO4(2-) for every 1 mmol of H2AsO4- and 0.24 mmol of OH- that has been sorbed. As(V) replaced SO4 up to half of the total SO4 in schwertmannite. The quantitative relationship among the three chemical compositions indicated that As(V)-sorbed schwertmannite would behave as a solid solution between the As(V) free schwertmannite and schwertmannite containing the maximum level of As(V). The equilibrium constant for the anion exchange in the solid-solution reaction estimated from the reacted solution chemistry depicts the As(V) content found in precipitates formed in acid mine drainage and laboratory experiments. Although schwertmannite is metastable with respect to goethite, the transformation is significantly inhibited by sorption of As(V). The solid-solution reactions also explain the stabilization of schwertmannite by sorption of As(V).