Biopolymer cassava starch(ST)-chitosan(CS)/montmorillonite(MMT) nanocomposites were prepared in which MMT was used as nanofiller and diluted acetic acid was used as solvent for dissolving and dispersing cassava starch, chitosan and MMT. XRD and TEM results indicated the formation of an exfoliated nanostructure of ST-CS/MMT nanocomposites. Mechanical properties testing revealed that at the range of the MMT content from 1wt% to 5wt%, tensile strength of the composites increased from 30MPa to 37.5MPa. But the elongation at break fall from 28% to 22% with the increasing of MMT. Obviously, MMT had an enforced effect to the composites. TGA results showed that the nano-dispersed MMT improved the thermal stability of the matrix systematically with the increasing of MMT.