Palladium-catalyzed denitrative/dechlorinated C-N coupling reactions of nitroaromatics/chloroarenes with hydrazines/hydrazones were performed using sterically bulky N-heterocyclic ligands (NHC = 2-aryl-5-(2,4,6-triisopropylphenyl)-2,3-imidazolylidene[1,5-a]pyridines). A range of N-arylbenzophenone hydrazones/hydrazine derivatives were obtained in good to excellent yields. This protocol provides an efficient method for the preparation of hydrazones/hydrazines via C-N coupling of inexpensive nitroarenes and chloroarenes.