An original method of preparation of enzyme collagen membranes has been developed which enables the asymmetrical coupling of multienzymatic systems working in sequence. One or several enzymes are immobilized on one face of the acyl-azide activated membranes, another enzyme being bound on the other face. When the first enzymatic face is exposed to the adequate reaction mixture, the products diffuse through the collagen membrane and act as substrates for the enzyme present on the other side. This possibility has been applied to the design of new and polyvalent multienzyme electrodes.