Palladiumnanoparticles stabilized with tris‐imidazolium tetrafluoroborates catalyze the stereoselective hydrosilylation of internalalkynes in a dry inert atmosphere to give (E)‐vinylsilanes in excellent yields. In the presence of controlled amounts of water a transfer hydrogenation reaction takes place with the formation of (Z)‐alkenes or the corresponding alkanes.