1-(Methylthio) and 1-(phenylthio)vinyllithiums were prepared by the treatment of the corresponding 2-methoxyethyl sulfides with twice molar amounts of butyllithium in the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA). β-Alkylthio-β,γ-unsaturated alcohols were obtained in good yields by the reaction of the lithium salts with aldehydes.