The reaction of layered silicates like magadiite with the cetyltrimethylammonium cation (CTA) was studied using different CTA/Na molar ratios. The layered materials have been synthesized by traditional methods and the intercalation of the lamellar material followed the conventional ion exchange procedure by controlled introduction of different amounts of surfactants as spacers in the lamellar structure. After the introduction of the surfactant molecules, two more steps are necessary to obtain the Pillared Interlayered Clays (PILCs): (i) the introduction of the pillarizing agent which is responsible for the growth of interlamellar pillars and (ii) the calcination process. Characterizations were carried out by different techniques to probe the effects of interlayer amounts of surfactant. X-ray diffraction showed that small amounts of surfactant are enough to increase the interlayer space to the maximum attainable by this process. The evolution of the structural order was probed through solid-state nuclear magnetic resonance (SSNMR) techniques. Finally, surface analyses indicated variations in the shape of mesopores at different CTA loadings.