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In this study, cellulose acetate (CA) mixed-matrix membranes were fabricated through the wet-phase inversion method. Two types of montmorillonite (MMT) nanoclay were embedded separately: sodium montmorillonite (Na-MMT) and organo-montmorillonite (O-MMT). Na-MMT was converted to O-MMT through ion exchange reaction using cationic surfactant (dialkyldimethyl ammonium chloride, DDAC). Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) compared the chemical structure and composition of the membranes. Embedding either Na-MMT and O-MMT did not change the crystallinity of the CA membrane, indicating that the nanoclays were dispersed in the CA matrix. Furthermore, nanoclays improved the membrane hydrophilicity. Compared with CA_Na-MMT membrane, CA_O-MMT membrane had a higher separation efficiency and antifouling property. At the optimum concentration of O-MMT in the CA matrix, the pure water flux reaches up to 524.63 ± 48.96 L∙m⁻²∙h⁻¹∙bar⁻¹ with over 95% rejection for different oil-in-water emulsion (diesel, hexane, dodecane, and food-oil). Furthermore, the modified membrane delivered an excellent antifouling property.