© 2016 The effects of the amylose content and the preparation sequence in physicochemical properties of starch/montmorillonite (MMT) composites were studied in this work. Native (30%) and high amylose Hylon VII (70%) starches were considered for assessing the effects of amylose content. Glycerol and MMT were used as additives to evaluate the effects of the former as plasticizer and the latter as reinforcer. The glycerol was incorporated before (Method M1) and after (Method M2) the addition of MMT. FTIR studies indicated that water bonding was affected by amylose content. Sorption isotherms indicated that method M2 favoured water adsorption and method M1 reduced water adsorption due to competition for active sites for interaction. TGA showed that method M1 induced a higher degradation rate than method M2. Wettability analysis by contact angle measurements showed that plasticizer promoted the hydrophilicity of the film, whereas MMT promoted a hydrophobic surface for both cases of amylose content.