Abstract: Coatings are disclosed that include a solvent and a silk fibroin and/or a silk fibroin-like macromolecule. These coatings are provided via self-assembly on a target surface, or co-assembly with one or more functionally active additive compounds such as organic or inorganic therapeutics. Coating growth is facilitated by the addition of effective concentrations of kosmotropic agents, such as potassium phosphate, and provide coatings that are smooth on the nanometer length scale and free of inhomogeneities. Because the method grows the coating from the surface in a non-covalent bottom-up approach, it is suitable for coating surfaces that have high curvature or complex geometry, such as porous materials or those with nano or micron-scale diameter features. These coatings can be grown on both organic and inorganic surfaces without the need for specific covalent chemistry of the surface or activation of the surface by irradiation or chemical treatment.