The aim of extreme biomimetics is to design a bridge between extreme biomineralization and bioinspired materials chemistry, where the basic principle is to exploit chemically and thermally stable, renewable biopolymers for the development of the next generation of biologically inspired advanced and functional composite materials. This study reports for the first time the use of proteinaceous spongin-based scaffolds isolated from marine demosponge Hippospongia communis as a three-dimensional (3D) template for the hydrothermal deposition of crystalline titanium dioxide. Scanning electron microscopy (SEM) assisted with energy dispersive X-ray spectroscopy (EDS) mapping, low temperature nitrogen sorption, thermogravimetric (TG) analysis, X-ray diffraction spectroscopy (XRD), and attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy are used as characterization techniques. It was found that, after hydrothermal treatment crystalline titania in anatase form is obtained, which forms a coating around spongin microfibers through interaction with negatively charged functional groups of the structural protein as well as via hydrogen bonding. The material was tested as a potential heterogeneous photocatalyst for removal of C.I. Basic Blue 9 dye under UV irradiation. The obtained 3D composite material shows a high efficiency of dye removal through both adsorption and photocatalysis.