Mesoporous silica MCF and metalosilicates Nb/MCF-14 and Ce/MCF-14 were modified with anchoring of melamine followed by (3-chloropropyl)trimethoxysilane functionalization. The texture/structure parameters, chemical composition and surface properties of synthesized samples were investigated by XRD, N 2 adsorption/ desorption, XPS, UV -vis, TG, elemental analysis and 2-propanol dehydration and dehydrogenation, whereas the activity of obtained catalysts was tested in the Knoevenagel condensation between benzaldehyde and mal- ononitrile. The Knoevenagel reaction required the presence of basic active sites or a pair of acid -base active centers. The novelty of the presented work was the use of mesoporous cellular foam (MCF) also modified with niobium (Nb/MCF-14) or cerium species (Ce/MCF-14) as supports for melamine anchoring. The use of the mentioned supports allowed the investigation of the role of open structure of MCF and metal dopant on mel- amine loading, its stability and reactivity in the Knoevenagel condensation. The obtained results clearly de- monstrate that cerium and niobium species loaded into MCF increase significantly the efficiency of melamine loading as well as its stability. The anchoring of melamine to silica and metalosilicates increase the activity of this modifier as a result of formation of secondary amine species. The presence of defected ceria in Mel/Ce/MCF- 14 raises the basicity of anchored melamine due to the electron donating effect of ceria. Consequently, the amine species in melamine are more active in the Knoevenagel condensation than those in Mel/Nb/MCF-14 because niobium species do not change oxidation state as easily as defected ceria.