This article reports the synthesis of an anatase thin film bearing a unique, hierarchical nanofungus-like structure. The nanostructures were directly grown from a Ti substrate via a facile, one-pot hydrothermal reaction, thus rendering ease of catalyst separation, recycle and reuse. High-resolution images of field emission scanning electron microscope (FESEM) indicated presence of small titania nanoparticulates of ca. 20nm on the nanoflakes, which constitute to the final overall nanofungus-like morphology. Hydrothermal duration-progressive FESEM images illustrated evolution of the nanofungus-structure and provided some evidence of the probable mechanism in obtaining the final nanostructure. The crystallographic phases and orientation of the photocatalyst were investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Nitrogen adsorption–desorption isotherm indicated that the as-prepared catalyst possessed a mesoporous structure and a Brunauer–Emmett–Teller (BET) surface area of 102.1m 2 /g. Greater light absorbance as shown from the UV–vis diffuse reflectance spectra, denoted enhanced light harvesting effects for UV penetration, possibly induced by inherent mesopores. Surface elemental analysis by means of X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX) underlined purity of the titania sample with detected presence of only Ti and O in the sample. High resolution XPS scan of F 1s region revealed presence of fluoride ions adsorbed on the surface of TiO 2 , which promoted etching and surface fluorination within the acidic hydrothermal environment. The photocatalyst exhibited efficient photocatalytic degradation of Bisphenol A (BPA) under UV-A irradiation, in comparison with a Degussa P25 TiO 2 coated film. The mechanism behind UV photocatalytic degradation of BPA over TiO 2 was elucidated using charge-trapping species as diagnostic tools and evidence have shown hydroxyl radicals (OH) to be the predominant active species in associated oxidation processes.