The use of ligands to tune the reactivity and regioselectivity of transition metal‐based catalyst for silicon‐mediated organic synthesis (SiMOS) is an important topic and challenge in organosilicon chemistry and synthetic organic chemitstry. In this manuscript, the dual ligand platinum catalyst system was developed for the hydrosilylation of alkynes. It was found that regioselectivity enhancement was determined with combinational use of phosphine ligand (6a) and multifunctional Py‐BINMOL ligand (4a). The corresponding vinylsilanes were obtained in high yields and high regioselectivities.