A carboxymethyl starch (CMS) film was prepared by a process in which gelatinized CMS was dried, and subsequently treated with water-soluble carbodiimide in the presence of zein in 70% ethanol or 70% acetone to form acid-amide cross-linkages in order to increase the hydrophobicity of the surface of the film. A small amount of zein protein was found to be present on the surface of the zein-CMS conjugate (Zein-CMS) film, resulting in its insolubility in hot water, low water vapor permeability, and resistance to digestion with alpha-amylase and beta-amylase. Digestion of the Zein-CMS film with protease rendered the film readily water-soluble, suggesting conjugation with zein as an effective means of increasing the hydrophobicity of biodegradable starch-based articles.