Layered double hydroxides (LDHs) containing Mg2+ and Al3+ in the basic layers and NO-3 as an interlayer anion were synthesized by the method of coprecipitation (pH 10). By changing the Mg2+/Al3+ ratio (1.5-4.5), the charge density on the (NO 3
)-MgAl-LDH sheets was varied. After pillaring with Fe(CN )3-6 , which was based on an anion exchange process, the interlayer space became accessible. This was reflected in the large created surface areas and micropore volumes. The applied models for the calculation of the micropore size distributions (Maes-Zhu-Vansant and Horvath-Kawazoe) gave matching results, revealing narrow distributions for all the samples, with the majority of the pores smaller than 0.71 nm. A correlation was found between the Mg2+/Al3+ ratio and the resulting microporosity after pillaring. The optimal ratio was situated around 3.3, resulting in a pillared [Fe(CN ) 6
]-MgAl-LDH with a Langmuir surface area of 499 m2/g and a micropore volume between 0.158 ml/g (mPV min ) and 0.177 ml/g (mPV max
). As an alternative, direct coprecipitation of the pillared LDHs was evaluated. This one-step mechanism proved to be a method producing similar results. Taking all this into consideration, one can conclude that hexacyanoferrate(III ) complexes form ideal anionic pillars for the creation of microporous layered double hydroxides.