Nature Communications, Published online: 26 June 2026; doi:10.1038/s41467-026-74943-8 Cross-electrophile coupling between unactivated alkyl halides and alkynyl halides has long been challenged by reactivity mismatch and poor chemoselectivity. Here the authors report nickel-catalysed crosselectrophile coupling enabled by a tridentate ligand that controls the sequence of electrophile activation, allowing direct construction of alkynyl–alkyl bonds.