AbstractN‐heterocyclic carbene‐palladium(II) amine complexes bearing primary aryl‐ or alkylamines were synthesized. The prepared complexes were characterized by single crystal X‐ray diffraction as well as NMR spectroscopy. These complexes exhibited good catalytic activities for the Buchwald‐Hartwig amination reaction of aryl chlorides to afford arylated anilines under mild conditions. All reactions were carried out in air and all starting materials were used as supplied without purification. 21 expected coupling products were obtained in moderate to high yields under optimum conditions.