We are using thin films of cellulose nanocrystals to investigate the interfacial properties of precursor native cellulose at the molecular level. Related inquires about the nature of interactions in the cell wall are difficult to access by using native fibers. Therefore, smooth films of cellulose nanocrystals were prepared by Langmuir–Blodgett deposition on silica surfaces using DODA cationic surfactant as a carrier for transfer from the air/liquid interface to the solid surface. Swelling and adsorption of the constitutive building macromolecules as well as their degradative behaviors in the presence of enzymes were studied. By using QCM, SPR and AFM we investigated the effect cellulose nanocrystals with different morphologies and crystallinities. Our results were compared to those from amorphous cellulose substrates.