AbstractCellulose nanofibril/phenol formaldehyde (CNF/PF) composite films with high work of fracture were prepared by filtering a mixture of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidized wood nanofibers and water-soluble phenol formaldehyde with resin contents ranging from 5 to 20 wt%, followed by hot pressing. The composites were characterized by tensile testing, dynamic mechanical analysis, scanning electron microscopy, atomic force microscopy, thermo-gravimetric analysis, and moisture/water absorption. Neat CNF films had tensile stress and Young’s modulus of 232 MPa and 4.79 GPa, respectively. PF resin was found to be well dispersed in the composites, although the resin increased the roughness of the film surfaces. Hygroscopic capacities of the composites were dramatically reduced, as compared to neat films, in both high humidity environments and when soaked in water. The composites exhibited slightly reduced tensile strength with modestly increased storage modulus compared to neat CNF films. Remarkably, the work of fracture ranged from 20 to 27 MJ/m3, making these films among the toughest reported for cellulose nanocomposites.