This study attempts to construct a multi-layer titania with merits inherent from both one/three-dimensional nanostructures and phase junctions. A solution-based technique was adopted to fabricate a sandwich-like titania thin film with one/three-dimensional nanostructures. The film consisted of one-dimensional anatase/rutile nanorod arrays as the underlayer and three-dimensional rutile nanoflower arrays as the top layer, which were intercalated with a sol–gel anatase nanoparticulate layer. The surface morphology, phase composition and light absorption behavior were characterized in detail by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) pattern and UV-vis diffuse reflectance spectra (UV-vis DRS). When utilized to assist photodegradation of rhodamine B in water, the sandwich film possessed an efficiency significantly higher than the sum of those derived from three component films. The appropriate layer-by-layer alignment of nanostructured films is thus argued to be a feasible route to fabricate titania thin films with high photocatalytic activities.