In situ monitoring of the electrolyte/electrode interfacial processes, such as the oxygen reduction reaction (ORR), is crucial for the design of electrolytes for fuel cells. In this study, we investigate the electrochemical behavior of platinum electrodes in protic ionic liquids (PILs) by means of in situ Fourier-transform infrared spectroscopy coupled with cyclic voltammetry. The result provides direct evidence of the change of water at the Pt electrode surface due to Pt oxide formation and reduction. A decrease in the interfacial water was observed in the spectra upon the formation of the Pt oxide. Conversely, the local water concentration at the electrode surface increases if the Pt oxide is reduced and the ORR takes place. At the same time, more cations replace anions on the electrode. The ORR kinetics in the [TFSI]-based PILs is slower than in the [TfO]-based ones, which could result from a blockage of catalytic sites by the adsorbed [TFSI] anions. It suggests that reducing the anion adsorption on the platinum surface could provide an opportunity to enhance the ORR activity.