Using both β-diketone and malonamide organosilane derivatives and silica Si-HIPE macro-mesocellular foams (acronym refers to the High Internal Phase Emulsion process), organically modified silicates (ORMOSILs) with chelating functionality have been synthesized. The organic functionalities have been anchored to the silica porous networks by both a two-steps grafting method, relating to grafted gOrgano-Si(HIPE), and a one-step co-condensation process, relating to Organo-Si(HIPE). The loading of monoliths by lanthanides was performed by impregnation of an europium (III) salt in solution, leading to a new Eu3+@(g)Organo-Si(HIPE) hybrid foams series. The resulting materials have been thoroughly characterized via a large set of techniques such as SEM, TEM, SAXS, mercury intrusion porosimetry, nitrogen adsorption, FTIR and 29Si CP MAS NMR. Luminescence behavior of this Eu3+@Organo-Si(HIPE) series was also studied and the effects of environment and europium concentration will be discussed.