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This work consists of preparation and characterization of composites produced from thermoplastic starch (TPS) and high impact polystyrene (HIPS). Due to the immiscibility of the system (TPS/HIPS), it was necessary to incorporate concentrations of 1, 2 and 3% of an organophilic montmorillonite (MMT) to improve the properties of the mixtures, in particular their rigidity. The composites thus prepared were characterized using XRD, FTIR, mechanical test, degree of swelling in water and biodegradability. The results show that the addition of MMT improves the mechanical properties of the mixtures such as the tensile strength and the Young’s modulus by 5% and 10%, respectively. In contrast, the resilience of the system has significantly decreased. Moreover, for 3% of MMT, the composites biodegradability is enhanced by 15% when compared to the TPS/HIPS mixture without MMT.