Zinc oxide species grafted on mesostructured cellular foam (MCF) silica are investigated using a combination of experimental and theoretical techniques. MCF is modelled using a realistic amorphous silica surface model surface slab. The most energetically favorable complexes grafted on the silica surface were identified and characterized at the molecular level. The Zn metal center was found in tetrahedral coordination. Moreover, the Si-O-Zn-OH species is found to be stabilized in a 5 fold coordinated silicon with an unusual trigonal bipyramidal geometry. A mechanism for the grafting process of the metal species on the support is proposed.