The transition metal‐catalyzed cross‐coupling reaction with Fischer metal carbene intermediates bearing an electron‐rich alkoxyl or siloxyl group remains a big challenge due to the lack of readily available corresponding carbene precursors. Herein, we report the coupling of alkynes with the Fischer‐type copper carbene species bearing a α‐siloxyl group, which could be in situ generated from acylsilanes catalytically under photoirradiation and redox‐neutral conditions. The side‐arm modified bisoxazoline (SaBox) ligands prove to be crucial for this coupling reaction, which provides the corresponding alkynyl alcohol in high yields with remarkable heterocycle tolerance and broad substrate scope. The coupling of alkynes with the Fischer‐type copper carbene species has been achieved, by harnessing α‐siloxyl carbene intermediates that were in situ generated from acylsilanes. Mechanistic studies suggested that the side‐arm modified bisoxazoline (SaBox) ligands are crucial for this coupling reaction.