Electrodes of the composition Ti/TiO2,SbOx were obtained by single-stage plasma electrolytic oxidation in aqueous electrolytes with antimony hydroxocomplexes. The surface morphology and composition of TiO2,SbOx layers deposited on titanium were studied by scanning electron microscopy, X-ray diffraction analysis, and X-ray photoelectron spectroscopy. The obtained layers contain anatase TiO2 and up to 1 at % of antimony as Sb2O3 and Sb2O5. The resulting Ti/TiO2,SbOx electrodes were tested as pH sensors. They have close to Nernst electrode function in the pH range from 2 to 10 (53 ± 1 mV/pH). In the acid–base titration of strong (HCl) and weak (CH3COOH) acids with Ti/TiO2,SbOx electrodes, potential jumps are obtained that are not inferior in magnitude to the potential jump for a glass electrode. A possibility of using Ti/TiO2,SbOx electrodes to determine the alkalinity of technogenic waters is shown.