New multifunctional materials with both high structural and gas barrier performances are important for a range of applications. Herein we present a one-step mechanochemical process to prepare molybdenum disulfide (MoS2) nanosheets with hydroxy functional groups that can simultaneously improve mechanical strength, thermal conductivity, and gas permittivity of a polymer composite. By homogeneously incorporating these functionalized MoS2 nanosheets at low loading of less than 1 vol %, a poly(vinyl alcohol) (PVA) polymer exhibits elongation at break of 154%, toughness of 82 MJ/m(3), and in-plane thermal conductivity of 2.31 W/m K. Furthermore, this composite exhibits significant gas barrier performance, reducing the permeability of helium by 95%. Under fire condition, the MoS2 nanosheets form thermally stable char, thus enhancing the material's resistance to fire. Hydrogen bonding has been identified as the main interaction mechanism between the nanofillers and the polymer matrix. The present results suggest that the PVA composite reinforced with 2D layered nanomaterial offers great potentials in packaging and fire retardant applications. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 406-414