We report a new catalytic protocol for highly selective C–H arylation of pyridines containing common and synthetically versatile electron-withdrawing substituents (NO2, CN, F and Cl). The new protocol expands the scope of catalytic azine functionalization as the excellent regioselectivity at the 3-and 4-positions well complements the existing methods for C–H arylation and Ir-catalyzed borylation, as well as classical functionalization of pyridines. ...