We describe the strong and spontaneous adsorption of different polyoxometalates on a carbon filled polycarbonate electrode and on glassy carbon. The modification of the surface occurs by dipping the electrode in a polyoxometalate solution at open circuit. The resulting first monolayer of polyoxometalate is used to anchor an adlayer of cations like NH3+ (CH2)(x)NH3+, Hg-2(2+) or Ag+ by electrostatic interaction. In this latter case the subsequent reduction of the metal ions leads to the formation of a metal layer on top of the polyoxometalate layer. Generally the cationic adlayer can be used to adsorb a second polyoxometalate layer or other anions like PtCl62-. The repeated alternate adsorption of anions and cations by this simple dipping procedure leads to molecular sandwiches with high stability and interesting redox properties.