AbstractA number of aminosilanes derived from N‐methylaniline and chloroorganylsilanes were prepared and characterized. X‐ray structure analysis was performed on the crystalline derivatives Ph(Cl)Si(NMePh)2 (4a), HSi(NMePh)3 (2b), MeSi(NMePh)3 (3b), and Ph2Si(NMePh)2 (6b). The compounds were comprehensively characterized by 1H, 13C, 29Si NMR, and IR spectroscopy. Volatile derivatives were further characterized by GC/MS. It was shown using quantum chemical methods that the planarization of the nitrogen atoms in the amino derivatives is caused by phenyl groups and silyl substituents.