A straightforward and reproducible synthesis of crack-free large-area thin films of 3D hexagonal (R-3m) mesostructured nanocrystalline titania (meso-nc-TiO2) using a Pluronic triblock copolymer (P123)/1-butanol templating system is described. The characterization of the films is achieved using a combination of electron microscopy (high-resolution scanning electron microscopy and scanning transmission electron microscopy), grazing-incidence small-angle X-ray scattering, in situ high-temperature X-ray diffraction, and variable-angle spectroscopic ellipsometry. The mesostructure of the obtained films is found to be based upon a 3D periodic array of large elliptically shaped cages with diameters around 20 nm interconnected by windows of about 5 nm in size. The mesopores of the film calcined at 300 °C are very highly ordered, and the titania framework of the film has a crystallinity of 40 % being composed of 5.8 nm sized anatase crystallites. The film displays high thermal stability in that the collapse of the pore architecture is incomplete even at 600 °C. The accessible surface area of 3D hexagonal meso-nc-TiO2 estimated by the absorption of methylene blue is nearly twice as large as that of 2D hexagonal meso-nc-TiO2 at the same annealing temperature.