The aminofluorosilane 1 (Me3C)2SiFNHSiMe(CMe3)2 is formed by treatment of (Me3C)2SiF2 with (Me3C)2MeSiNHLi. The lithium derivative of 1, (Me3C)2SiFLi(THF)2NSiMe(CMe3)2, 3, is formed by treatment with n-C4H9Li. Treatment of 3 with Me3SiCl gives Me3SiF, LiCl and the iminosilane (Me3C)2(THF)Si = N-SiMe(CMe3)2, 4. Compound 4 can be distilled and recrystallized from benzene. Its crystal structure has been determined.