Syntheses of Na-magadiite were performed under hydrothermal conditions in a water/alcohol medium. It is only possible to obtain a pure and well crystallized magadiite sample using a water/ethanol medium at a water/ethanol molar ratio of ~0.12. As shown by thermal analysis and 1H liquid nuclear magnetic resonance spectroscopy, ethanol is not incorporated into the magadiite. Intercalation of dodecyl- and hexadecyltrimethylammonium cations in the interlayer space of Na-magadiite at different theoretical ion-exchange rates shows that the experimental ion- exchange rates are in good agreement with the theoretical ones. However, scanning electron micrographs of the sample having a theoretical ion exchange rate of 25–75% shows that the exchanges are not homogeneous (both thin and thick platelets are present). Attempts to obtain a Si- pillared compound starting from C16TMA-magadiite as the host material leads to a microporous compound having a BET surface area of 778 m2g−1.