Ni(II) complexes supported by tridentate N^N–^N diarylamido pincer-type ligands have been demonstrated to act as active catalysts in the carbon–carbon bond forming alkylation of azoles using unactivated alkyl halides. Here, we show that benzannulated phenanthridine-containing ligands can form homogeneous Ni(II) catalysts active with both benzoxazole and benzothiazole substrates. These precatalysts have been fully characterized in solution and the solid state, including by cyclic voltammetry.