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Ni–Zr0.82Y0.18O1.91 (YSZ) and Ni–La0.90Sr0.10ScO2.95 (LSS) cermets for solid oxide and protonic ceramic electrochemical cells were studied by means of H/D isotope exchange with the gas phase equilibration method for the first time. The experiments were carried out at 2 mbar of dry hydrogen in the temperature range of 400–800 ᵒC. The three parallel channels of hydrogen surface exchange were found to exist in both Ni-YSZ and Ni-LSS cermets. The mechanism of hydrogen isotope exchange for Ni-YSZ was found to be temperature independent, while, in the case of Ni-LSS, the mechanism changed with temperature and was more complicated at lower temperatures (400–600 °C). It was revealed that hydrogen spillover was the rate-determining step for both cermets. The electrochemical kinetics of hydrogen oxidation were studied on symmetric cells with a YSZ supported electrolyte and Ni-YSZ electrodes and with an LSS supported electrolyte and Ni-LSS electrodes in a wet (3 vol % H 2O) hydrogen atmosphere at 1 atm. The mechanism of hydrogen oxidation on the Ni-LSS electrode differs from that of the Ni-YSZ electrode. It changes with temperature and is also more complicated at a lower temperature range. © 2021 Elsevier B.V.