The amine moiety is an important functionality for many applications such as enzyme immobilization on porous solid supports. In this study, mesoporous SBA-15 was functionalized by co-condensation of tetraethoxysilane (TEOS) with organosilane (aminopropyl)triethoxysilane (APTES) in a wide range of molar ratios of APTES:TEOS in the presence of triblock copolymer P123 under acidic synthetic conditions. The functionalized materials were characterized by physical adsorption, CHN elemental analysis, and various spectroscopic techniques. The data of FTIR, elemental analysis, XPS, and solid-state NMR demonstrated the incorporation of amine functional groups on the surface and inside the pore walls of the APTES-functionalized SBA-15 samples. The results of SAXS, N-2 adsorption, and TEM showed the effect of APTES present in the initial synthesis mixtures on the formation of SBA-15 mesostructure such as structural ordering, pore size, and surface area. Reasons behind the observed strong adverse effect of APTES on SBA-15 mesostructure were investigated.