4-Chlorobenzenesulfonate (4-CBS) was intercalated between layers of Zn–Al layered double hydroxides (LDHs). Two methods of incorporation were applied: (1) direct synthesis by coprecipitation of metal nitrates and sodium 4-CBS and (2) ion exchange of the LDH nitrate with the organic ion. The solids were characterized by X-ray diffraction and infrared spectroscopy. The direct method, effected at different pH values, led to a hybrid material with good degree of intercalation. In order to optimise the exchange conditions, particular attention was given to the effect of solution pH, 4-CBS/NO 3 ratio and exchange temperature. The total exchange was successful and a new stable hybrid nanostructured material was obtained at pH 8 and with a 4-CBS concentration of 0.0028M. This solid was further characterised by chemical and thermal analyses.