Flower-like TiO 2 nanostructures were successfully synthesized via the urea homogeneous precipitation method using (NH 4 ) 2 TiF 6 as a titanium source in aqueous solution. This approach was simple, environmentally friendly and without using template. The flower-like TiO 2 nanostructures were characterized in detail with scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV–vis spectrum, respectively. The flower-like TiO 2 nanostructures, with diameters ranging from 150–300nm, were assembled by primary nanoparticles and the length of the petals was approximately 60nm. Interestingly, the surface of the flower-like TiO 2 nanostructures appeared to have many pores with diameters of 10–13nm after the sample being calcined at 550°C, while the morphologies and sizes of the TiO 2 samples did not change. The photocatalytic activity of the as-prepared samples was evaluated by photo-degradation of rhodamine B (RhB) from aqueous solution at ambient temperature. The flower-like porous TiO 2 samples exhibited much higher photocatalytic activity than the flower-like TiO 2 samples. All these advantages showed a bright future for this flower-like porous photocatalyst in environmental protection.