Based on previous work related to the design and application of rigid tridentate phosphine‐pyridine‐phenyl coordination offered by a PNC‐pincer ligand upon cyclometalation to nickel, the synthesis, spectroscopic and solid state characterization and redox‐reactivity of two NiII(PNC) complexes featuring either a methyl (2CH3) or CF3 co‐ligand (2CF3) are described. One‐electron oxidation is proposed to furnish C‐C reductive elimination, as deduced from a combined chemical, electrochemical, spectroscopic and computational study. One‐electron reduction results in a ligand‐centered radical anion, as supported by electrochemistry, UV‐spectroelectrochemistry, EPR spectroscopy and DFT calculations. This further attenuates the breadth of chemical reactivity offered by such PNC‐pincer ligands.