A two-step anodizing process was used to prepare wide-range highly ordered porous anodic alumina membrane (PAA) in the electrolyte of oxalic acid. The effects of anodic voltage,anodizing time,size of aluminium foil and additives on the regularity of PAA membrane were also studied in the process of two-step anodization. The template method was combined with the sol-electrophoresis deposition and sol-gel method respectively to prepare highly ordered titania nanostructures. The diameter and length of the obtained nanostructures were determined by the pore size and depth of the PAA template. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the morphology and phase structure of the PAA template and the titania nanostructures. The results show that the anodizing time and the additive of ethanol have a great effect on the regularity of PAA template. This can be explained from the self-organized process and the current density theory. A theoretical model based on the self-organized process was established to discuss the formation mechanism of PAA template from the chemical perspective. The titania nanostructures prepared with this method has a high specific surface area. Furthermore,the photocatalytic activity of titania nanostructures on methyl orange were studied. Compared with ordinary titania membranes,the titania nanostructures synthesized with this method have higher photodegradation activity.