Ruthenium (II) metallodendrimer (RuDen) and the wheel-shaped Cu-20-Tungstophosphate [Cu20Cl(OH)(24)(H2O)(12)(P8W48O184)](25-) heteropolyanion (HPA) were successfully immobilised on a glassy carbon electrode through employment of the Layer-by-Layer (LBL) deposition method. The fabricated (Cu20P8W48/RuDen) multilayer films have been investigated with cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and surface based techniques. The layers exhibited well behaved redox activity for both the HPA and RuDen moieties and exhibited good stability towards redox cycling and associated thin layer behaviour. The charge transfer resistance (R-ct) and Warburg Impedance (Z(w)) obtained values for the layers by EIS indicated an increase the compactness of the layers upon construction. The (Cu20P8W48/RuDen) multilayer films exhibited electrocatalytic ability towards the reduction of iodate.