Nanocomposites based on 10 to 60 vol % cellulose nanofibers (NFC) in a photopolymerizable hyperbranched acrylate matrix were prepared. Unmodified NFC and NFC chemically modified with a silane coupling agent and with ceric ammonium nitrate for direct polymer grafting from the cellulose surface were used. A homogeneous dispersion of NFC in the matrix was obtained in each case, leading to a marked improvement in oxygen barrier (up to nine times) and thermomechanical properties (storage modulus increased up to seven times). The mechanisms involved in the permeability reduction were investigated, revealing non-monotonic trends in the evolution of the solubility and diffusion coefficients with NFC content. Most significantly, the inherent moisture sensitivity of the oxygen permeability of the NFC was found to be drastically reduced when it was dispersed in the polymer matrix, particularly after chemical modification, underlining the promise of the present approach for the production of robust, high barrier organic films. (c) 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40604.