Dimethylphenylsilyllithium undergoes conjugate addition to a variety of α,β-unsaturated enones in the presence of sub-stoichiometric amounts of dimethylzinc. Down to 10 mol % of Me 2 Zn facilitates these reactions to afford good to excellent yields of β-silylated products. This catalytic behavior is displayed when the Me 2 Zn used is generated in situ from the addition of methyllithium to zinc (II) iodide or when used directly from a commercial source. This methodology in which sub-stoichiometric quantities of the reactive organometallic reagent are present at a given time may provide a route for catalytic enantioselective conjugate addition of trialkylsilyl moieties to enones.