In the presence of a silyl triflate and an amine base, a nickel–phosphine complex catalyzes the direct conjugate addition of ethylene, α-olefins, and aryl alkenes to unsaturated aldehydes and ketones. The enolsilane products are isolated in good to very high yield, and in very high stereoselectivity for some cases. The alkene is a functional equivalent of an alkenylmetal reagent in the transformation.