The bottom-up approach in designing and synthesis of materials using nanoparticles of different size-, shape- or chemical composition is an extreme challenge. However, in this way, new task-specific or general use nanocomposites can be obtained. This work presents, the investigations of the preparation procedures and molecular stability of Langmuir films based on cellulose nanocrystals (CNC) and different liquid crystals. The CNC-based nanocomposite with the 5CB, 5OCB, 5FCB, and 5PCH liquid crystals, have been obtained by the modified Langmuir technique. The investigations of the Langmuir monolayers gives an excellent model system for studying intermolecular interactions at the interface, which allows analyzing the ordering, sorption, desorption, association and phase separation phenomena determining physical and chemical properties of studied systems. The process of self-assembly and molecular organization on the air-liquid interphase was studied for different compositions of LC/CNC films. The compressibility profiles and the mean molecular area have been calculated. The stability of prepared monolayers has been studied to investigate the sorption and desorption processes. The morphology of the prepared systems was determined by Brewster Angle Microscopy (BAM), and the influence of the CNC on LC organization in molecular monolayers on the air-liquid interphase has been studied.