The palladium(II) dinuclear complex with bridging cyclometalated phosphines, {Pd 2 [μ-(C 6 H 4 )PPh 2 ] 2 (μ-O 2 CCH 3 ) 2 } (Pd 2 L 2 ), having a paddlewheel structure, is reversibly oxidized in CH 2 Cl 2 to a dinuclear palladium(III) analogue via two successive one-electron steps. Solid state voltammetry of Pd 2 L 2 in contact with aqueous electrolytes produce as one-electron oxidation with two competing mechanisms involving anion intercalation/anion binding between/to metal centres, chloride ions acting as inhibitors for the first pathway. R- and S-Pd 2 L 2 produces a significant stereoselective electrocatalytic activity with respect to the oxidation of l- and d-glutamic acid in alkaline media.