We report the synthesis of highly porous hybrid silica-polyacrylamide aerogels where the inorganic network was obtained through the hydrolysis and poly-condensation of tetramethoxysilane via a two-step sol–gel process while the polyacrylamide polymer was made by photocopolymerization of two organic monomers, the acrylamide and the bis-acrylamide. These aerogels were obtained after a carbon dioxide supercritical drying while the corresponding xerogels were dried by simple evaporation. These materials, as well as pure silica and polyacrylamide aerogels and xerogels, were characterized by FTIR spectroscopy, solid-state 29Si and 13C NMR spectroscopy, Thermogravimetric Analysis, a nitrogen adsorption desorption technique, and Scanning Electron Microscopy. The FTIR and NMR spectra and the TGA/DTA analyses confirm the coexistence of highly branched silica and polyacrylamide networks reflecting the hybrid nature of the materials obtained. Nitrogen adsorption measurements reveal high specific surface areas and pore size distributions disclosing the mesoporous character of these hybrid materials. Hybrid silica-polyacrylamide aerogels having a specific surface area equal to 572 m2/g and a pore volume 1.92 cm3/g were successfully prepared for the first time in this study. The high porosity of these aerogels is due to a better resistance of the silica network to capillary forces during the supercritical drying when silica coexists with a polyacrylamide network.