The new N‐heterocyclic carbene (NHC) complex [PdCl2{(CN)2IMes}(PPh3)] (2) ({(CN)2IMes}: 4,5‐dicyano‐1,3‐dimesitylimidazol‐2‐ylidene) and the NHC palladacycle [PdCl(dmba){(CN)2IMes}] (3) (dmba: N,N‐dimethylbenzylamine) have been synthesized by thermolysis of 4,5‐dicyano‐1,3‐dimesityl‐2‐(pentafluorophenyl)imidazoline (1) in the presence of suitable palladium(II) precursors. The acyclic complex 2 was formed by ligand exchange using the mononuclear precursor [PdCl2(PPh3)2] and the palladacycle 3 was formed by cleavage of the dinuclear chloro‐bridged precursor [Pd(μ‐Cl)(dmba)]2. The new NHC precursor 1‐benzyl‐4,5‐dicyano‐2‐(pentafluorophenyl)‐3‐picolylimidazoline (5) was formed by condensation of pentafluorobenzaldehyde with N‐benzyl‐N′‐picolyldiaminomaleonitrile (4). The NHC palladacycle [PdCl2{(CN)2IBzPic}] (6) ({(CN)2IBzPic}: 1‐benzyl‐4,5‐dicyano‐3‐picolylimidazol‐2‐ylidene) was prepared by in situ thermolysis of 5 in the presence of [PdCl2(PhCN)2]. The three palladium(II) complexes were characterized by NMR and IR spectroscopy, mass spectrometry and elemental analysis. In addition, the molecular structures of 2 and 3 were determined by X‐ray diffraction. The π‐acidity of (CN)2IBzPic was compared with (CN)2IMes and perviously reported π‐acidic imidazol‐2‐ylidenes by NBO analysis. The Mizoroki–Heck (MH) reactions of various aryl halides with n‐butyl acrylate were performed in the presence of complexes 2, 3 and 6. The new precatalysts showed high activity in the MH reactions giving good‐to‐excellent product yields with 0.1 mol‐% precatalyst. The nature of the catalytically active species of 2, 3 and 6 was investigated by poisoning experiments with mercury and transmission electron microscopy. It was found that palladium nanoparticles formed from the precatalysts were involved in the catalytic process.