The design and fabrication of strong, lightweight, and damage-resistant composite materials are major topics of studies on composites. Biomimetics, a developing multidisciplinary field, is now leading the fabrication of novel materials with remarkable mechanical properties. Graphene oxide (GO), a graphene derivative, possesses good mechanical properties, a high aspect ratio, and good solubility in aqueous solutions, indicating great potential in nanocomposite fields. In this work, bioinspired layered GO/poly(vinyl alcohol) (PVA) nanocomposite films with remarkable mechanical performances are prepared by an environmental friendly, bottom-up assembly methodology. The structural analysis shows alternate piles of inorganic GO platelets and organic PVA binder. Tensile tests indicate that the borate-treated GO/PVA nanocomposite films display 360 MPa of strength, which is twofold to threefold higher than that of biological materials (e.g., nacre). Toughness of GO/PVA nanocomposites is also enhanced fourfold compared with nacre. To reveal the toughening function of the intercalated polymer in the nanocomposites, the influence of polymer with varied molecular weights (Mws) on the fracture mode of the nanocomposites is systematically investigated through quasi-static tensile and creep tests. The PVA molecules with a higher Mw can connect more neighboring GO platelets through inter- and intra-linkages than those with a lower Mw, resulting in efficient stress transfer along the GO plane direction. Thus, tensile strength and toughness are improved. This work illustrates the functions of bonding types between inorganic–organic phases and intercalated polymers with different Mws on the mechanical properties of the layered nanocomposites, including stiffness, strength, and toughness.