Dehydrogenative silylation of primary and secondary amines with triphenylsilane was catalyzed by ytterbium-imine complexes, [Yb(eta(2)-Ph2CNAr)(hmpa)(n)], to give aminosilanes in good yields. In the reaction with diphenyl- and phenylsilanes, diaminosilanes were formed as major products. Whereas n- and sec-alkylamines were readily silylated, tert-alkylamines and aromatic amines exhibited lower reactivities. Moreover, hydrosilylation of imines has been achieved by using phenylsilane and the imine complexes (Ar = Ph, C6H4F-4), giving rise to mono- and diaminosilanes. The two reactions were in agreement as regards the product selectivities and yields.