A strategy for the stepwise formation of organic/inorganic multilayered films is presented. Structurally ordered, alternating stacks of a cationic organic polymer and anionic sheets of an inorganic mineral are produced with lattice spacings as low as 1.5 nm, architectures which have a great potential in the design of, for example, optical elements and sensors. The method allows the close control of the deposited thickness of the layers and is applicable to a wide variety of materials.