Sequential adsorption of a cationic polyelectrolyte and individual sheets of the silicate mineral hectorite has allowed controlled, stepwise formation of multilayered films on silicon wafers. Each component adsorbs rapidly by an ion-exchange mechanism, and x-ray diffractometry indicates structural order even in films with thicknesses greater than 0.2 micrometer. The large lateral extent of the silicate sheets (about 25 to 35 nanometers) allows each layer to cover any packing defects in the underlying layer, thus preserving structural order in the growing film. With careful choice of component materials, this method should allow for the preparation of multilayered films with a variety of technologically important properties.