Pincer-type ligands are believed to be very robust scaffolds that can support multifarious functionalities as well as highly reactive metal motifs applied in organometallic chemistry, especially in the realm of catalysis. In this paper, we describe the redox and, therefore, noninnocent behavior of a PNP (PNP- = N[2-P(CHMe2)(2)-4-methylphenyl](2)) pincer ancillary bound to nickel. A combination of structural, spectroscopic, and theoretical techniques suggests that this type of framework can house an electron hole when coordinated to Ni(II).