Iron centres incorporated in silicate frameworks or located in their pores have been shown to possess unique catalytic properties. As compared to aluminosilicates this area of zeolite chemistry is much younger and in the first part of this review the findings made so far are summarised. Molecular model compounds may help to understand the formation, corrosion and reactivity of such materials or to even develop new ones. Hence, the subsequent parts deal with molecular iron siloxides, the number of which is still quite limited, and their behaviour also in relation to the iron‐modified zeolites is outlined. At first, compounds based on an incompletely condensed cubic silsequioxane are discussed, before iron(III) complexes of more basic siloxide ligands with varying steric demands are described. Finally, recent developments based on branched polydentate siloxides are presented.