Zein has the unique ability to form a viscoelastic protein network, similar to gluten, upon hydration and shearing above its glass transition temperature. In the present work, confocal Raman microscopy, and small and large deformation rheological tests were used to study the interactions and structures driving zein and gluten network formation. Starch (80% w/w), protein (20% w/w) (composed of different proportions of zein and gluten) and water were mixed into a viscoelastic dough mass at 40 °C. Results showed that, although, the zein-rich dough samples exhibited higher extensibility and resistance to deformation, these samples had undesirable weaker elastic behavior (low G’ and G*, and low creep recovery percentage) according to rheological tests. The high resistance to extension of zein-rich dough samples was attributed to the β-sheet-rich fibrils that are stabilized by extensive hydrogen bonding. Confocal Raman microscopy also confirmed the described fibrillar network structure of zein. In addition, strong positive correlations were found between the tyrosine doublet intensity ratio (Raman), intermolecular β-sheets, and elastic properties of the dough samples. Based on the data obtained at different length scales, a model was proposed for the zein structure in a viscoelastic dough system.