Abstract: The exchange of Ca2+ and Na+ by tanthanide ions (Ln3+ = Pr3+, Gd3+, Er3+) in montmorillonite was investigated at two different ionic strengths (0·01 and 0·1 mol/kg). Preferential sorption of Ln3+ was observed and variable selectivity coefficients were found depending upon the lanthanide concentration in the solid, and ionic strength. The highest exchange extent of Ln3+ always occurred for the system Na+/Ln3+, but the exchange selectivities of Ln3+ were generally higher in the exchange system Ca2+/Ln3+. Although the relative affinity of montmorillonite for the three lanthanide ions was similar, distinctive behaviour between Pr3+ and the heavier lanthanides, Gd3+ and Er3+, was noted. The study of Ln3+ adsorption in trace amounts showed specific adsorption of lanthanides at high concentrations of Na+ in the external solution and that the exchange stoichiometries in the interlayer regions were 3 : 1 at equilibrium pH = 4.