The direct functionalization of alkyne triple bonds using a radical strategy provides an efficient platform for creating a wide range of substituted alkenes. However, developing a multicomponent enantioselective radical reaction using feedstock alkynes to forge all-carbon quaternary stereocenters─while addressing challenges related to compatibility, selectivity, and efficiency─remains relatively rare. Here we report an enantioselective electrochemical nickel-catalyzed three-component cross-coupling of readily available terminal alkynes, diverse racemic alkyl radical precursors, and group transfer reagents (such as (TMS)