A [Cp*Rh(III)]-catalyzed electrophilicamination of arylboronic acids with diethyl azodicarboxylate (DEAD) was developed, and arylhydrazides were produced in excellent yields and selectivity. The analogous amination with the arylazocarboxylates afforded the corresponding N,N-diarylhydrazides. The electrophilicamination of arylboronic acids with azocarboxylates proceeds readily under mild conditions