Treatment of 1-propynylsilanol 1a with two equivalents of tert-butyllithium in THF in the presence of HMPA at -78 °C afforded silylpropynyllithium 2a bearing an anionic oxygen on the silicon atom. The reaction of 2a with various electrophiles gave acetylenic adducts in good yields. Higher regioselectivities were achieved in the reaction of silyl-substituted propynyllithium derived from potassium silanolate.