Disclosed herein are polypeptide multilayer films comprising a hybrid polypeptide comprising a first polypeptide segment and a second segment, the two segments being covalently joined by one or more non-peptidic linkages. The first segment comprises a polypeptide having a magnitude of net charge per residue of greater than or equal to 0.4, and a length of greater than or equal to about 12 amino acid residues. The second segment comprises a polypeptide or another polyelectrolyte.