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The changes in the physical characteristics of ball milled corn starch (BMS) after chemical modification were investigated. The SEM and XRD analysis of BMS granules showed a fragmented aspect with a total loss of their initial crystallinity and an increase of their potential hydroxyl substitution sites. This morphology facilitated the access of the esterifying solvents into the starch molecule as corroborated by the spectacular increase of the water solubility index (WSI) and water absorption index (WAI). Following the acetylation, the degree of substitution (DS) increased up to 2.83 with the augmentation of the iodine catalyst content (p = 0.011). However, under the same condition of esterification, the DS of the BMS was slightly lower in comparison to the control, due to an increase in the number of free hydroxyl groups. Consequently to the modification, a reduction in the Tg, strong hydrophobicity and important exo‐corrosion affecting the granules were noticed.