There is great technological interest in the design of multifunctional microporous materials, particularly those with pores in the 10–20 Å range. The many attempts to achieve this goal through cross-linking zirconium phosphate-like layers by use of several types of diphosphonic acids will be described. A variety of functionalized pillared materials are also described with potential as sorbents and catalysts. The advances in synthetic methods now achieved promises to produce a wide variety of porous materials with controlled pore sizes and varying degrees of hydrophilic–hydrophobic character whose chemical behavior will be mediated by the incorporation of diverse functional groups as part of the pillars.