Adsorption of cations (Na+, Ca2+, Ba2+) onto negatively charged (pH 10.4) hematite (alpha-Fe2O3) particles has been studied. The oxide material was carefully prepared in order to obtain monodisperse suspensions of well-crystallized, quasi-spherical particles (50 nm in diameter). The isoelectric point (IEP) is located at pH 8.5. Adsorption of barium ions onto oxide particles was carried out and the electrophoretic mobility was measured throughout the adsorption experiment. Comparison with calcium adsorption at full coverage reveals a higher uptake of Ba2+. In both cases it shows also that chloride ions coadsorb with M2+ ions. Simultaneous uptake of the positive and negative ions explains why the electrophoretic mobility does not reverse to cationic migration. A theoretical study of the surface speciation has been carried out, using the MuSiC model. It reveals the presence of negative as well as positive sites on both sides of the point of zero charge (PZC) of the hematite particles, which may explain the coadsorption of Ba2+ and Cl-at pH 10.4. The effective charge of the oxide particles, calculated from the electrophoretic mobility, is in very good agreement with the results found with the MuSiC modelization and the chloride/barium adsorption ratio. It also verifies the theory of ionic condensation. Calorimetric measurements gave a negative heat for the overall reaction occurring when Ba2+/Cl-ions adsorb onto hematite. Despite the fact that anions (Cl-and OH-) adsorption onto mineral oxides is an exothermic phenomenon, it is likely that barium and calcium adsorption is endothermic, denoting the formation of an inner-sphere complex as reported in the literature.