A theoretical study of the accessibility of hexacoordinate palladium(VI) compounds is presented. Species such as [Pd(SiR3)(6)], [PdCl6], and [Pd(OH)(6)] are predicted to be unstable toward reductive elimination of the ligands. In contrast, the presence of a stable palladium(VI) center is expected in [PdF6], a low-spin nearly octahedral molecule with a weak Jahn-Teller distortion and highly covalent Pd-F bonds. A vibrational analysis confirms such a geometry as an energy minimum, and a special distribution of its spin density makes PdF6 a highly interesting synthetic target.