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Cellulose nanowhiskers (CWs) extracted from cotton fibers were successfully modified with distinct anhydrides structures and used as additives in poly(vinyl alcohol) (PVA) nanocomposite films. The surface modification of CWs was performed with maleic, succinic, acetic or phthalic anhydride to compare the interaction and action the carboxylic groups into PVA films and how these groups influence in mechanical properties of the nanocomposites. CWs presented a high degree of crystallinity and good dispersion in water, with average length at the nanoscale. The addition of specific amounts (3, 6 and 9 wt.%) of modified-CWs increased up to 4.4 times the storage modulus (PVA88-CWSA 9 wt.%), as observed from dynamic mechanical analysis (DMA), compared to the bare PVA films. A significant increase in mechanical properties such as tensile strength, elastic modulus, and elongation at break showed a close relationship to the amount and chemical surface characteristics of CWs added, suggesting that these modified-CWs could be explored as reinforcement additives in PVA films., (Copyright © 2018 Elsevier Ltd. All rights reserved.)