This work extensively covers the use of layer-by-layer (LbL) assembly of polyelectrolytes for the transduction of catalytic and affinity events. It is demonstrated that by controlling the charge of polyelectrolytes, electrostatic interactions drive then the LbL construction of supramolecular architectures with improved performance. Particularly, by adequately charging an osmium based redox polymer, a multicofactor protein (fructose dehydrogenase) may be deposited in a favored orientation resulting in a more efficient electrochemical communication. A H 2 O 2 transducing interface is created by the enhancement of electrostatic interactions between the electrochemical and catalytic layer. Further assemblies include the coupling of an oxidase (alcohol oxidase) with the H 2 O 2 transducing interface resulting in a linear increase of current with the number of AOX layers. Finally, affinity assemblies are demonstrated by deposition of anti Dexamethasone antibodies. Faraday currents are then obtained by the electrochemical communication between the HRP labeled immunoconjugate and the electrochemical interface in a heterogeneous competitive assay format.