Platinum(II) complex [Pt(ItBu0)(ItBu)][BArF4] (1a) is a highly active and selective catalyst in the dehydrocoupling of amines and silanes at part-per-million catalyst loadings (up to 10 ppm, 0.001 mol%), achieving the highest TON and TOF numbers reported in the literature (up to 1 mmol scale). NMR studies suggest a process taking place through electrophilic activation of the silane by the platinum species, assisted by an amine.