Electrode surface modification by organo-inorganic layered coatings can be achieved readily by drying a completely delaminated laponite clay sol mixed with polycationic silasesquioxane oligomers. Oligosilsesquioxanes were synthesized by hydrolytic polycondensation of trialkoxysilanes bearing an alkylamino or alkyltrimethylammonium function. Films of excellent quality with exceptional adhesion and mechanical properties can be obtained. The intercalation of organosiloxane oligomers is accompanied by the expansion of the him and by the existence of a mesoporosity as shown by XRD measurements and N-2 adsorption experiments. The ion-exchange properties of the resulting coatings as well as permeation of neutral molecules were studied in aqueous and non-aqueous electrolytes as a function of the oligomer loading. For oligomer loadings higher than the cation-exchange capacity (cec) of laponite, the coatings behave as anion-exchangers which allows the binding a wide range of redox anions. Incorporated anions remain electroactive not only in aqueous but also in non aqueous electrolytes as a consequence of a fixed pore size and permanent interlayer spacing of oligomer-expanded laponite. On the other hand intercalation of oligomers allows us to modulate the permeability of the coating as shown by permeation experiments using neutral electroactive probes in non aqueous electrolytes. In the held of electroanalysis, amperometric biosensors made by the entrapment of glucose oxidase inside the hybrid material have been investigated successfully. Such enzymatic films exhibit enhanced analytical performances as compared with those obtained using native sodic laponite. The potential applications of this new hybrid material in the field of electrocatalysis have been exemplified by the electroprecipitation of catalytic nanoparticles such as Pt(0) obtained from the incorporation of the anionic precursor PtCl42-.