The microstructure of hybrid silica xerogels synthesized by the base-catalyzed polymerization of tetraethoxysilane (TEOS) in ethanol in the presence of 3-aminopropyltriethoxysilane (AES) and of 3-(2-aminoethylamino)propyltrimethoxysilane (EDAS) as co-reactants, and dried in subcritical conditions, is analyzed. A thorough structural characterization of the samples is performed combining nitrogen adsorption, small-angle X-ray scattering (SAXS), and transmission electron microscopy coupled with digital image analysis. The use of these methods shows that, for both co-reactants, the xerogels are made of macropores supported by filaments, with each filament being formed of smaller structures. The quantitative impact of the additive on each structural level is assessed. The data are compared with a previous time-resolved SAXS study conducted during the formation of the gels (J. Phys. Chem. B 2004, 108, 8983-8991). The results are analyzed in the framework of a double phase separation model.