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The supersilylated ethene trans-(tBu3Si)HC=CH(SitBu3) (triclinic, P ī) is accessible from the reaction of tBu3SiCHBr2 with nBuLi at −78 °C in THF or Et2 O. The reaction of Li(H2NCH2CH2NH2)C≡CH with tBu3SiBr leads to the formation of (tBu3Si)C≡CH and (tBu3Si)C≡C(SitBu3). X-Ray quality crystals of (tBu3Si)C≡C(SitBu3) (triclinic, P ī) were obtained by recrystallization from hexane. In contrast to the structures of the disilane tBu3Si-SitBu3 and the disiloxane tBu3Si-O-SitBu3, the sterically crowded ethene trans-(tBu3Si)HC=CH(SitBu3) and ethyne (tBu3Si)C≡C(SitBu3) feature dihedral angles of 60° in the solid-state structures.