Titanium dioxide has been successfully synthesized via an evaporation-induced self-assembly method. Here, TiCl4 was chosen as a precursor and CTAB as a surfactant. The SEM images revealed that hydrochloric acid, added during reaction, obviously enlarges the particle size of TiO2 since a larger size was obtained. The X-ray diffraction (XRD) results confirmed the appearance of both the anatase and rutile structures of TiO2 after titania film was calcined at 450°C for 1 hour. The TEM results showed that the evaporation temperature had no significant impact upon the particle size of TiO2.