Tuning the architecture of multilayer nanostructures by exploiting the properties of their constituents is a versatile way to develop multifunctional films. Herein, we report a bottom-up approach for the fabrication of highly ordered hybrid films consisting of dimethyldioctadecylammonium (DODA), iron decorated polyhedral oligomeric silsesquioxanes (POSS), and montmorillonite clay platelets. Clay platelets provided the template where Fe/POSS moieties were grafted by the use of the surfactant. Driven by the iron ions present, DODA adopted a staggered arrangement, which is essential to realize the controllable layer-by-layer growth of the film. The elemental composition of the film was studied by X-ray photoelectron spectroscopy and X-ray reflectivity confirmed the existence of smooth interfaces between the different layers.