This paper presents a spin-coating layer-by-layer assembly process to prepare multilayered polyelectrolyte-clay nanocomposites. This method allows for the fast production of films with controlled layered structure. The preparation of a 100-bilayer film with a thickness of about 330 nm needs less than 1 h, which is 20 times faster than conventional dip-coating processes maintaining the same hardness and modulus values. For validation of this technique, nanocomposite films with thicknesses up to 0.5 μm have been created with the common dip self-assembly and with the spin coating layer-by-layer assembly technique from a poly(diallyldimethylammonium)chloride (PDDA) solution and a suspension of a smectite clay mineral (Laponite). Geometrical characteristics (thickness, roughness, and texture) as well as mechanical characteristics (hardness and modulus) of the clay-polyelectrolyte films have been studied. The spin-coated nanocomposite films exhibit clearly improved mechanical properties (hardness 0.4 GPa, elastic modulus 7 GPa) compared to the “pure” polymer film, namely a sixfold increase in hardness and a 17-fold increase in Young’s modulus.