Alkenyl N-pivaloylhydroxamates undergo an Ir(III)-catalyzed diamination of the alkene with simple exogenous secondary amines under extraordinarily mild reaction conditions. The regioselectivity of the diamination is controlled by the solvent and the electronics of the cyclopentadienyl (Cp-x) ligand on Ir. On the basis of a set of mechanistic experiments, we propose that the relative rates of Ir(V)-nitrenoid formation versus attack on the amido-Ir-coordinated alkene by the exogenous amine determine the outcome of the reaction.