Six samples of titanium dioxide of different phase compositions and specific surface areas have been characterized by XRD, Raman-and FTIR spectroscopy, adsorption of nitrogen, electrophoresis. Adsorption of Zn(II) ions at the TiO2/NaCl aqueous solution interface as well as the effect of adsorption on the structure of electrical double layer have been studied. The influence of ionic strength, pH and presence of ions on the adsorption of Zn(II) ions at the TiO2/NaCl solution interface have also been investigated. The zeta potential, surface charge density, parameters of adsorption edge pH50% and ΔpH10–90% for different concentrations of basic electrolyte have been determined. Studied unpurified samples showed lower values of isoelectric point pHiep compared with literature data due to the presence of anion impurities. The antibate dependence between pHiep values and particle size has been established. Adsorption of Zn(II) ions using monophase samples is completed at a lower pH than for the biphase TiO2. Appearance of the point CR3 is associated with the charge turnover from positive to negative at high values of pH and formation of Zn(OH)2.