An excellent supersilylation agent, supersilyl triflate, tBu3SiO3SCF3, is easily obtained from tBu3SiH and CF3SO3H. Supersilyl triflate, tBu3SiO3SCF3, reacts with lithium amide or lithium hydrazide to form the supersilyl amine, tBu3SiNH2, or the supersilyl hydrazines, tBu3SiNHNH2 and tBu3SiNH-HNSitBu3, respectively. The structures of supersilyl triflate, tBu3SiO3SCF3, and bissupersilyl hydrazine, tBu3SiNH-HNSitBu3, have been determined by X-ray structure analysis.