Hypotheses: Montmorillonite, an abundant raw material, is a good candidate to obtain textured nanocomposites. However, the resulting structure of the composite depends on the dispersant used. This work aims at investigating the effect of organic polysaccharides, namely carboxymethylcellulose (CMC) or chitosan (Ch) differing by their side groups, on the resulting structure of montmorillonite-based nanocomposites. Experiments: The effect of sodium hexametaphosphate and of two polysaccharide derivatives (carboxymethylcellulose and chitosan) combined with montmorillonite on the structure and microstructure of resulting composite films was investigated using particle size analysis, rheological measurements, thermogravimetric analysis, X-ray diffraction, scanning electron microscopy and flexural properties measurements of the textured films. Findings: Results showed that the film structure and microstructure depend on the additive. The high organization (and resulting toughness) of the montmorillonite/sodium hexametaphosphate films results from an exfoliated then layered microstructure, whereas the addition of polysaccharide derivatives leads to the particle agglomeration. In this case, two mechanisms are in competition: surface adsorption and intercalation between exfoliated platelets. (C) 2013 Elsevier Inc. All rights reserved.