The effects of sintering atmosphere on the properties of symmetric TiO2 membranes are studied with regard to sintering behavior, porosity, mean pore size, surface composition, and surface charge properties. The experimental results show that the symmetric TiO2 membranes display better sintering activity in the air than in argon, and the mean pore diameters and porosities of the membrane sintered in argon are higher than those of the membrane sintered in the air at the same temperature. The surface compositions of the symmetric TiO2 membrane sintered in the air and in argon at different temperatures, as studied by X-ray photoelectron spectroscopy, are discussed in terms of their chemical composition, with particular emphasis on the valence state of the titanium ions. The correlation between the valence state of the titanium ions at the surface and the surface charge properties is examined. It is found that the presence of Ti3+ introduced at the surface of the symmetric TiO2 membranes by sintering in a lower partial pressure of oxygen, is related to a significant decrease in the isoelectric point. TiO2 with Ti4+ at the interface has an isoelectric point of 5.1, but the non-stoichiometric TiO2-x with Ti3+ at the interface has a lower isoelectric point of 3.6.