A new method to prepare pillared zirconium clay modified by sulfate was developed. This method was based on adding sulfates to zirconium species before the pillaring process. First the intercalation solution was studied by 1H NMR, conductivity and potentiometric techniques and the effect of the reflux on this solution was examined. The intercalated clay was then characterized by DRX, N2-BET adsorption, chemical analysis and mass spectrometry. On the base of the solution study and the solid study we can propose that intercalated species are more probably octameric polycations with an advance hydrolysis degree. The addition of sulfate ion on the intercalation solution gives more than a single mode of interaction between SO42− and Zr-polycation. The resulted intercalated clay shows a good thermal stability of the texture and of the retained sulfur.