A series of “abnormal” NHC ligand precursors based on imidazopyridines and their corresponding NHC-palladium diiodide complexes were prepared. Our study included the first report on a palladium complex with an abnormal NHC ligand derived from imidazo­[1,5-a]­pyridine. DFT calculation on the free ligands confirmed the higher electron-donating properties of the abnormal NHC ligands than their normal NHC isomers. The structural properties of all the complexes were studied in detail by single-crystal X-ray diffraction studies, revealing that, in general, Pd–carbene bond distances in palladium complexes with abnormal NHCs were longer than those in their isomers with normal NHCs. A significant trans influence is observed in the palladium complexes with abnormal NHC ligands. But in the complexes with normal NHC ligands, both Pd–carbene and Pd–N bond distances are short. Catalytic studies revealed that the palladium complexes were very efficient in catalyzing direct C–H arylation between 1,2-dimethylimidazole and aryl halides using a low Pd loading of 0.5 mol %. The difference in catalytic activity between the normal and abnormal isomers is, however, small.