Cationic and anionic LC ionomers, which possess both thermotropic and lyotropic phases, are suitable materials to fabricate multilayers with an internal structure. The LC ionomers were synthesized using a reactive precursor polymer and used for the multilayer buildup by solution-dipping and spin-coating methods based on the electrostatic attraction between polycations and polyanions. Multilayers prepared by the spin-coating method were thicker and showed a smoother surface than the ones prepared by the solution-dipping method. The multilayers prepared by the solution-dipping method showed, on the other hand, a better internal order with respect to layering and orientation of the mesogens, as a result of the liquid crystalline phase. The LC ionomers and multilayers thereof were fully characterized by NMR, UV, IR, DSC (differential scanning calorimetry), XRR (X-ray reflectometry), SPR (surface plasmon resonance), AFM (atomic force microscopy), and polarizing microscopy analyses.