The elaboration of organosilica-based hybrid monoliths exhibiting a hierarchically structured bimodal porous structure with chelating functionality have been synthesized under interplay between high internal phase emulsion (HIPE) and lyotropic mesophases. For the first time grafted Eu3+@g -diketone-Si(HIPE) and Eu3+@gmalonamide-Si(HIPE) hybrid foams have been synthesized while a related Eu3+@ -diketone- Si(HIPE) material has been obtained under a one-step co-condensation process. The loading of monoliths with lanthanides was performed by impregnation of an europium(III) salt in solution. The resulting materials have been thoroughly characterized via a large set of techniques including scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray scattering (SAXS), mercury porosimetry, nitrogen sorption isotherms, Fourier transform infrared (FTIR) spectroscopy, and 29Si and 13C magic angle spinning nuclear magnetic resonance (MAS NMR). This new series of luminescent Eu3+ containing Organo-Si(HIPE) materials has a large potential of promising applications in catalysis, optics, sensors, chromatographic supports, and so forth. For the first time, optical properties of these versatile materials with macro- and microporosity have been addressed thorough their absorption and emission spectra along with their relaxation luminescence properties.