The aminated silica gels SiO2/SOCl2/NH3 (I), SiO2/SiCl4/NH3 (II), SiO2/BCl3/NH3 (III), and SiO2/γ-aminopropyltriethoxysilane (SiO2/APTES, IV) have been synthesized. According to DRIFT spectroscopy and chemical analysis data, the surface amino groups of I–III are “free,” while those of IV interact with the surface OH groups of the silica gel and with one another. The strength of basic sites has been measured on the proton affinity (PA) scale as the shift of the ν(CD) band of adsorbed deuterochloroform. The basicity of an aminated silica gel depends on its chemical composition. Silica gel IV (PA = 938 kJ/mol) is a stronger base than I–III (PA = 829 kJ/mol). As the basicity of the NH2 group decreases, the N-H stretching band shifts to higher frequencies.