In the presented work, a significant increase in the tensile strength of the PVA composite material is reported. The obtained best value of 122 MPa and 14.6% swelling shows the excellent synergistic effect of both crosslinker and reinforcement material. The composite films were prepared by simple mechanical dispersion of reinforcement material, bacterial cellulose nanowhiskers (BCNW) into PVA solution followed by crosslinking with diacids, succinic acid (SuA), and adipic acid (AdA). The effect of aliphatic carbon chain length of crosslinker on thermal, mechanical, and water uptake properties is evaluated and discussed in detail. Neat PVA had the strength of 37.3 MPa. With 5% reinforcement of BCNW, that is, without crosslinking, it exhibited 97% increase, that is, 74.5 MPa. With crosslinking of 15 mmol of SuA and AdA PVA films for 2 h had excellent thermal properties with swelling percentage of 19 and 26.6% and tensile strength of 103 and 67 MPa, respectively. The best result obtained was for 5% BCNW-PVA films crosslinked with 15 mmol SuA. These results were explained on the basis of synergetic crosslinking and extended hydrogen bonding between PVA and reinforcement material. The composite films can be used as biological implants, a membrane for pervaporation and filtration system, etc. (C) 2016 Wiley Periodicals, Inc.