An unsymmetrical pincer N-heterocyclic carbene–nitrogen–phosphine (CNP) and its palladium complexes PdCl2(κ2-CP) (4) and [PdCl­(κ3-CNP)]­PF6 (5·PF 6 ) were synthesized. NMR spectra disclosed that the transformation of complex 4 structure occurred in the solution. Further NMR experimental and single crystal structure analysis of complex 4 provided unequivocal and structural evidence for the formation of complex [PdCl­(κ3-CNP)]Cl (5·Cl) in the solution of complex 4. The catalytic performance of palladium complexes 4 and 5·PF 6 was investigated with the direct Csp2–H arylation of benzoxazoles with aryl bromides. Notably, aryl bromides could give up to 97% arylation products in the presence of 0.5% complex 4. For ortho-substituted substrates, the steric hindrance had a significant impact, but product yields could be improved remarkably by extending reaction time. This result implied the catalytic active species in this system was stable and kept in a long lifetime. The flexible backbone and unsymmetrical pincer structure with a flank N-heterocyclic carbine should be a feasible strategy to realize an efficient catalytic transformation. This simple catalyst system first realized the direct arylation of aryl bromides with a catalyst loading as low as 0.25% without excessive base and copper as assistant catalyst.