A hydride and a silyl group of hydrosilane is introduced into 1,3-divinyldisiloxane in the presence of a catalytic amount of (eta(5)-C5H5)Fe(CO)(2)Me. Instead of the product expected from the well-known hydrosilylation reaction, the product obtained is that characteristic of dehydrogenative silylation at one vinyl group and hydrogenation at the other vinyl group of 1,3-divinyldisiloxane. Based on deuterium labeling experiments, a catalytic cycle for this new reaction has been proposed.