A new ionic salt, cis‐[Pd(L)(PPh3)(H2O)2](SO3CF3)2 (A), in which L is an amido‐functionalized N‐heterocyclic carbene (NHC) ligand, has been prepared by the salt metathesis reaction between [Pd(L)(PPh3)Cl2] and AgOTf in wet acetonitrile. It was successfully characterized by NMR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction analysis. Complex A was found to be effective in catalyzing the double C–H functionalization of various nitrogen‐ and sulfur‐containing heteroarenes to form fused polycyclic heteroaromatic compounds with alkynes in the presence of Cu(OAc)2 and tetra‐n‐butylammonium bromide. Indoles, thiophenes, imidazo[1,2‐a]pyridine, and imidazoles were used as substrates. In particular, intriguing imidazo[5,1,2‐cd]indolizine compounds could be obtained under the conditions employed.