Large-scale biomimetic organic/inorganic hybrid nanocoatings with a nacre-like microstructure were prepared via a facile co-assembly process. Different from conventional polymer nanocomposites, such nanocoatings contain a high concentration of nanosheets, which can be well aligned along the substrate surface. Moreover, the nanosheets and polymer matrix can be chemically co-crosslinked. As a result, the nanocoatings exhibit exceptional mechanical properties (high stiffness and strength), barrier properties (to both oxygen and water vapor), and flame retardancy, but meanwhile they are highly transparent (maintaining more than 85% of their original transmittance to visible light). The nanocoatings can be applied to various substrates and regular or irregular surfaces (e.g., films as well as foams). Because of their excellent performance and high versatility, such nanocoatings are expected to find widespread application.