The aluminium amide Al(NMe₂)₃ acts as a stoichiometric or catalytic reagent in dehydrogenic Si–N bond formation using amines and silanes. Although of limited substrate scope, this represents the first p-block metal catalytic system for N–H/Si–H dehydrocoupling. The observed catalytic rate law for the formation of aminosilane products in a model study of one of the catalytic reactions suggests a mechanism involving the silane component in the deprotonation of the amine (possibly in the form of a hypervalent silicon hydride).