Given the broad use of nanostructured crystalline titania films, an environmentally friendly and more sustainable synthesis route is highly desirable. Here, a water-based, low-temperature route is presented to synthesize nanostructured foam-like crystalline titania films. A pearl necklace-like nanostructure is introduced as tailored titania morphology via biotemplating with the use of the major bovine whey protein ß-lactoglobulin (ß-lg). It is shown that titania crystallization in a brookite-anatase mixed phase is promoted via spray deposition at a comparatively low temperature of 120 °C. The obtained crystallites have an average grain size of (4.2 ± 0.3) nm. In situ grazing incidence small-angle and wide-angle X-ray scattering (GISAXS/GIWAXS) are simultaneously performed to understand the kinetics of film formation and the templating role of ß-lg during spray coating. In the ß-lg:titania biohybrid composites, the crystal growth in semicrystalline titania clusters is sterically directed by the condensing ß-lg biomatrix. Due to using spray coating, the green chemistry approach to titania-based functional films can be scaled up on a large scale, which can potentially be used in photocatalytic processes or systems related to energy application.