Zein, the prolamine of corn, contains nearly an equal amount of hydrophilic and lipophilic amino acid residues. Its tertiary structure has a prismatic geometry of 17 nm x 4.6 nm x 1.2 nm. Zein structure allows it to function as a polymeric amphiphile. Zein had been observed to self-assemble into periodic bilayer structures and nanotubes. This work investigated the structural development of zein-HLB systems. The formation of several mesophases, including spheres, sponge and lamellae, were identified. Images were obtained by SEM, AFM, and FIB/SEM. The radius of curvature of observed assemblies was affected by the HLB of components in the system. Thus, lipophilic flavor oils, decreased the curvature of zein spheres producing smaller spheres. Curvature increased in the presence of amphiphilic fatty acids forming sponges with interconnected channels. Hydrophilic compounds increased curvature to the point of forming smooth films. The results of this study see a future in microencapsulation and controlled release systems for flavor and bioactive compounds in the food industry.