Abstract Aluminum-pillared-layered montmorillonites (PILMs) were tested for their potential application in the removal of copper or cesium from aqueous solutions. By varying the initial conditions, several PILMs were prepared and characterized by means of X-ray fluorescence (XRF), proton induced gamma-ray emission (PIGE), X-ray diffraction (XRD) and sorption isotherms. Uptake of metals was studied by means of XRF spectrometry for copper sorption or γ -ray spectrometry for cesium, using 137Cs as radiotracer. The sorption kinetics and capacity of PILMs were determined in relation to the effects of factors such as the initial metal concentration, initial pH of the solution and the presence of competitive cations. Kinetic studies showed that an equilibrium time of few minutes was needed for the adsorption of metal ions on PILMs. A pseudo-first-order equation was used to describe the sorption process for either copper or cesium. The most effective pH range for the removal of copper and cesium was found to be 4.0–6.0 and 3.0–8.0, respectively. Cesium sorption isotherms were best represented by a two-site Langmuir model while copper isotherms followed the Freundlich or the two-site Langmuir model. Cesium sorption experiments with inorganic or organic competitive cations as blocking agents revealed that the high selective sites of PILMs for cesium sorption (1–2% of total) are surface and edge sites in addition to interlayer exchange sites. In copper sorption, the two sites were determined as interlayer sites of PILMs after restoring their cation exchange capacity and sites associated with the pillar oxides.