A new redox‐active 4,5‐bisguanidino‐substituted o‐benzoquinone ligand L is synthesized, which allows rational access to heterobinuclear complexes through the sequential coordination of two metals. In the examples discussed in this work, mononuclear Cu and Pd complexes are prepared in a first coordination step, and these complexes are then used as precursors to homobinuclear [CuII‐L0‐CuII] and heterobinuclear [PdII‐L0‐CuII] complexes. In the heterobinuclear complex, the PdII is coordinated by the softer bisguanidine side of L and the CuII by the harder dioxolene side (in line with the HSAB concept). The heterobinuclear complex is in a temperature‐dependent equilibrium with its dimer, with two unsymmetrical Cu‐Cl‐Cu bridges. The redox‐chemistry of the [CuII‐L‐CuII] and [PdII‐L‐CuII] complexes is studied. One‐electron oxidation of both complexes was found to be quasi‐reversible in CV experiments, and chemical one‐electron oxidation was achieved with NO+(SbF6−). In the case of the homobinuclear complex [L(CuCl2)2]+, intramolecular ligand–metal electron‐transfer, triggered by coordination of a CH3CN solvent molecule, leads to a temperature‐dependent equilibrium between the form [CuII‐L0‐CuIII] at low temperatures (with CH3CN coordinated to the CuIII atom) and [CuII‐L⋅+‐CuII] at higher temperatures (without CH3CN).