A solid-state and solution study to characterize the possible configurations of the [Pd(L)₂]²⁺ cations (L=dpp, dpq, ddpq) has been carried out. To accomplish this objective the homoleptic complexes [Pd(L)₂](hfac)₂ (L=dpp, dpq, ddpq; HFAC=hexafluoroacetylacetonate ion) were isolated. The syntheses were performed in diethyl ether by reacting [Pd(hfac)₂] with a two molar equivalent of the respective L ligand. Besides, X-ray quality crystals were obtained by metathesis with NH₄PF₆ to derive the hexafluorophosphate species [Pd(dpq)₂](PF₆)₂. The X-ray crystallographic study shows that the coordination sphere of the [Pd(dpq)₂]²⁺ cation is square planar and that the bidentate chelating dpq ligands are linked via their N-pyridine atoms. Furthermore, the cation structure reveals an intramolecular π–π stacking between the two quinoxaline rings in a “pincer-like” configuration. In CDCl₃ solution, the ¹H NMR spectra of the [Pd(L)₂](hfac)₂ complexes permit to infer the presence of a mixture of two isomeric forms with different populations. The results suggest that the predominant form being that of the solid-state “pincer-like”. For the less abundant species a configuration with the quinoxaline groups (dpq, ddpq) or pyrazine groups (dpp) in opposite side respect to the plane of the Pd(II) centre, “step-like”, is suggested. The preponderance of the “pincer-like” configuration was attributed to the influence of the aromatic π–π stacking interactions.