A novel NiH-catalyzed highly regioselective coupling of alkenes with vinyl chlorosilanes, constructing C-Si bonds, is developed. Under mild reaction conditions, a series of benzyl organosilanes with various functional groups could be accessed. Further synthetic studies illustrate that the products of this chemistry could be used as versatile precursors to prepare complicated organosilicon compounds. Moreover, the NiH-catalyzed mechanism of the present transformation was proposed based on control experiments.