Binary and ternary blends based on an organically modified bentonite, originated from Maghnia Algeria (OBT), poly (styrene‐co‐allyl alcohol) (PSAA) containing 40 mol% of allyl alcohol and cellulose acetate butyrate (CAB) of different ratios, are elaborated via solution intercalation method in tetrahydrofuran (THF) as solvent. These binary and ternary blends are investigated by X‐ray diffraction (XRD), scanning electron microscopy (SEM), FTIR spectroscopy, differential scanning calorimetry (DSC), and thermogravimetry analysis (TGA). Due to the occurrence of favorable specific interactions between the constituents of the blends, as evidenced by FTIR, PSAA40/CAB system is miscible in the whole composition range. Indeed, a single glass transition temperature (Tg), intermediate between those of the pure components is observed with each initial mixture. The effect of the organo‐clay and its dispersion within the blend matrix on the morphology and thermal behavior of the miscible PSAA/CAB blends of different ratios and of their corresponding ternary hybrids blends is discussed. The Tg of the ternary blends increased by 5–10 °C compared with their corresponding virgin blends. Significant improvement of thermal stability of ternary hybrids compared to their virgin ones was evidenced by TGA.