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Porous, noncrosslinked polyelectrolyte-complex thin films (see figure), which will find applications in biomedicine, for example for drug or gene delivery, are achieved by using a simple, mild, and efficient method. Layer-by-layer assembly of polyanion and a blend of two polycations is followed by removal of the reductively degradable polycation template in the multilayered film in dithiothreitol solution.