Dehydrogenative silylation of olefins, such as styrenes, methyl acrylate, and vinyl ether, using allyltriethoxysilane as the source of the silyl group can be catalyzed by RuHCl(CO)(PPh3)(3) to give the corresponding vinylsilanes in good to excellent yields. The ruthenium complex also catalyzed the self-dehydrogenative silylation of allylsilanes, yielding 1,3-bis(triorganosilyl)propenes.