A series of well‐defined (NHC)Pd(N–heterocyclic carboxylate)(OAc) complexes (N–heterocyclic carboxylate = pyridine‐2‐carboxylate, quinoline‐2‐carboxylate and isoquinoline‐1‐carboxylate) were synthesized and fully characterized by NMR spectra, HR‐MS and X‐ray single crystal diffraction. The obtained complexes were then used for direct C2‐arylation of free (NH)‐indoles with arylsulfonyl hydrazides. With low catalyst loading, all complexes exhibited high catalytic activities for the arylation reactions.