A functionalised Fe-substituted Keggin Na-14[Fe-4(C2O4)(4)(H2O)(2)(SbW9O33)(2)]center dot 60H(2)O type POM termed "Fe(4)Ox(4)" has been successfully immobilised onto carbon electrode surfaces through the employment of conducting polypyrrole films and the layer-by-layer (LBL) technique. For the POM doped polypyrrole films the redox systems associated with the POM's tungsten-oxo framework was not apparent upon redox cycling, however a reversible redox couple associated with the Fe-III/II redox system was clearly seen within the pH range 2-7. Organised multilayer assemblies were constructed by the employment of the layer by layer (LBL) technique through alternating anionic Fe(4)Ox(4) layers and cationic Ru-II metallodendrimers with poly(diallyldimethylammonium chloride) (PDDA) employed as an initial base layer. Stable redox couples associated with both the Fe-III/II and tungsten-oxo framework, for the Fe(4)Ox(4) POM, and the Ru-III/II for the metallodendrimer, were clearly observed upon layer construction and redox switching within the pH domain of 2-7. The resulting multilayer assembly showed good stability towards redox cycling. Further investigations into the multilayer assembly were undertaken by determining it is charge transfer resistance using AC-impedance voltammetry. The layer also showed catalytic ability towards the reduction of H2O2 at pH 6.5. (C) 2011 Elsevier Ltd. All rights reserved.