Abstract: | Several cobalt complexes bearing tridentate (NNN) ligands were synthesized and served as precatalysts for alkyne hydrosilylation with Ph2SiH2. For terminal alkynes, the catalyst L2 b‐CoCl2 was selected, and resulted in the corresponding α‐vinylsilanes with high (Markovnikov) regioselectivity and extensive functional‐group tolerance. For internal diaryl alkynes, the catalyst L2 c‐CoCl2 exhibited the best activity, and afforded E‐selective vinylsilanes through syn‐addition in excellent yield under mild conditions. |