Thanks to the +PCy3 substituents which are unlikely to undergo intramolecular C–H activation, the Pd(II) complex [(C,C,C)PdCl](OTf) having a neutral LX2-type NHC, diphosphonium bis(ylide) pincer ligand was selectively prepared by a double deprotonation of the [(NHC)PdCl2(Py)] precursor with tBuOK. The influence of the +PCy3 substituents on the overall electronic properties of this pincer scaffold was evaluated by IR spectroscopy data of the corresponding Pd–CO adduct, revealing its stronger electron-donating character in comparison to the structurally related NHC core pincer bearing +PPh3 extremities. Treatment of the electron-rich pincer complex [(C,C,C)PdCl](OTf) with AgOTf led to the C,C-chelating NHC-phosphonium ylide Pd(II) complex [(C,C)Pd(OTf)Cl](OTf) via the oxidatively induced homolytic cleavage of a Pd–ylide bond. In the presence of a stronger base (KHMDS or LDA) cyclometalation of a +P–Cy substituent was observed, affording a constrained Pd(II) complex featuring the unique anionic LX3-type C,C,C,C-NHC, diphosphonium tris(ylide) ligand.