We demonstrate the controlled formation of highly-ordered rare-earth stearate multilayer Langmuir-Blodgett films, novel supramolecular organized structures: hybrid polyanion/rare-earth metal cation/anionic surfactant metal-organic superlattice thin films with separating acidic amphiphile bilayers by highly rare-earth-doped polymeric interlayers and fabrication of closely packed, homogeneous and stable rare-earth metal cation/polyanion complex self-assembled multilayer films in which molecular polyelectrolyte building blocks are held together by complexed polyvalent metal cations. The design and fabrication strategies developed to construct those films are based on the surface and interface trivalent rare-earth metal cation complexation with consecutive formation of multilayer superstructures on the solid substrates. The structure and morphology of the built-up multilayer films were characterized by atomic force microscopy and X-ray diffraction.