Clay materials play a key role in determining the retention capacity of a soil, and are widely used in waste treatments. One of the most commonly used clays is palygorskite. The aim of this research is to determine the chemical species formed by Zn when retained in a palygorskitic clay material. Adsorption isotherm analysis is useful in studying the retention process, because it provides a macroscopic view of the retention phenomena. Complementary techniques are needed in order to study the different retention processes. Sorption isotherms of Zn on palygorskitic clay were carried out; the supernatant was analysed by means of dynamic light scattering (DLS) and the residues by using X-ray diffraction (XRD), scanning electron microscopy-energy dispersive angle X-ray (SEM-EDAX) analysis and extended X-ray absorption fine structure (EXAFS). Isotherm analysis shows that the global retention process could be due to the sum of two separate processes, adsorption and surface precipitation via solid-solution. This is supported by DLS, which shows that ζ potential increases as the Zn(II) is retained onto clay surfaces but remains constant during the precipitation process. The XRD pattern corresponding to the Zn-clay system showed weak new peaks, probably from zincite. The microanalysis by X-ray fluorescence of several spots selected for their different electronic densities indicated that the retained Zn was randomly distributed across the clay surface. Analysis by EXAFS supports the hypothesis of retention via adsorption and solid-solution surface precipitation.