Unsupported titania membrane without pinholes or cracks was prepared by sol-gel techniques from alkoxide starting materials. The influence of the amount of PVA additives in the gel preparation process was studied by thermal analysis, function group analysis, and x-ray diffraction analysis. The prepared membranes were characterized by different methods. The results show that the exothermic reactions between PVA and titania gel occurred at lower calcination temperatures, strengthening the gel network during the process. The PVA as well as calcination temperature can be used to control the microstructure properties of the titania membrane top layer. The results after calcination at 400degreesC for 4 hours show that the sharp degree of pore size distribution increases with the PVA/TiO2 ratio rising, ending at a 18.7 wt% ratio.