Pillared clays are interesting materials with applications in catalysis and adsorption processes. To obtain these materials, several preparation procedures are necessary and must be optimized to tune the final properties of the resulting pillared clay. Therefore, this article reports the influence of synthesis parameters (temperature and concentration) of Keggin-Al13 polycations and different intercalation times (0.5 up to 72 h) on the structural properties of Al-pillared clays. The natural clays are from Brazil, and they are composed mainly of montmorillonite. By XRD, N2 sorption, XRF and 27Al NMR results of the Al-PILCs, we verified that the pillaring solution could be prepared at room temperature with an aging time of 24 h. For the cation exchange process, a period of at least 2 h is necessary to ensure the formation of pillared materials. The concentration of the Keggin-Al13 polycations was evaluated by using diluted pillaring solutions followed by applying re-pillaring procedures. After submitting the pillared clay to another pillaring process, the number of pillars in the interlamellar space increased; however, the micropore volume decreased concomitantly. Thus, by optimizing the synthesis conditions of the Keggin-Al13 polycations, Al-PILCs could be obtained with good values of basal spacing and specific surface area.