Metal oxide interfaces are suitable functional materials for various energy applications. For example, TiO2 can act not only as an anode material in new generation photovoltaic and energy storage technol-ogies, but also in the photocatalytic production of hydrogen. For such applications, a controlled mor-phology on distinct length scales is particularly important to fulfill optimal performance conditions. Furthermore, a high interfacial area and, hence, a high surface-to-volume ratio of nanostructured TiO2 is beneficial for devices. Industrial-relevant deposition methods, such as spray coating, are applicable to fabricate intended morphologies by low-cost solution processing via diblock copolymer-directed sol-gel synthesis. When it comes to an industrial scale, however, limiting factors affecting sustainability are the commonly involved organic solvents. Water-soluble biopolymers can replace synthetic copol-ymers to facilitate sustainable production. The bovine whey protein ß-lactoglobulin (ß-lg) can act as a template in water-based TiO2 synthesis forming aggregates of different structures by denaturing at dif-ferent pH values. In this work, biohybrid films are obtained from solutions with decreasing pH using spray deposition. Bulk and surface-sensitive grazing-incidence small-angle neutron scattering (GISANS) investigations yield an understanding of the influence of pH on the biohybrid film’s mor-phologies. Real-space imaging complement the obtained results.