The surface chemistry of a series of well-defined metalorganic ferrous and ferric iron complexes on periodic mesoporous silica (PMS) was investigated. In addition to literature known (FeN)-N-II(SiMe3)(2)](2)(THF), Fe-II[N(SiPh2Me2)(2)](2), and Fe-III[N(SiMe3)(2)](2)Cl(THF), the new complexes [Fe-II{N-(SiHMe2)(2)}(2)](2) and Fe-III[N(SiHMe2)(2)](3)(mu-Cl)Li(THF)(3) were employed as grafting precursors. Selection criteria for the molecular precursors were the molecular size (monoiron versus diiron species), the oxidation state of the iron center (II versus III), and the functionality of the silylamido ligand (e.g., built-in spectroscopic probes). Hexagonal channel-like MCM-41 and cubic cage-like SBA-1 were chosen as two distinct PMS materials. The highest iron load (12.8 wt %) was obtained for hybrid material [Fe-II{N(SiHMe2)(2)}(2)](2)@MCM-41 upon stirring the reaction mixture iron silylamide/PMS/n-hexane for 18 h at ambient temperature. Size-selective grafting and concomitantly extensive surface silylation were found to be prominent for cage-like SBA-1. Here, the surface metalation is governed by the type of iron precursor, the pore size, the reaction time, and the solvent. The formation of surface-attached iron ligand species is discussed on the basis of diffuse reflectance infrared Fourier transform (DRIFT) and electron paramagnetic resonance (EPR) spectroscopy, nitrogen physisorption, and elemental analysis.