Cyclic voltammetric measurements on thermally coated Ti/TiO2 electrodes in 0.05 -3.0 M H2SO4, Na2SO4 and NaOH media were carried out to evaluate the cause of pH sensitivity of these electrodes. The electrode activity decreased in the order H2SO4 > NaOH > Na2SO4. Ionic strength had a significant influence on the electrode activity. In the redox catalysis of nitrobenzene reduction the pH dependence increased significantly. The electrode activity again decreased in the same order. In acid media the TiO2 surface is protonated. In alkaline media OH- ions are specifically adsorbed on the TiO2 surface. The concentration of these charged species, as well as the ease of counter ion transport through the charged layers during surface redox reactions in the oxide layer, is identified as the cause of the pH sensitivity of the electrodes. In acid media proton transport in the him occurs through a ’surface Grothus’-like mechanism. In alkaline medium proton abstraction by OH- ions from the trapped H2O molecules may facilitate proton transport.