Traditionally the protonic conductivity in these materials is measured by indirect methods. For example, conductivity measurements in mixed gas atmospheres, comparing for example dry N2 with humidified N2, thereby allowing the contribution of protons to be evaluated. In this study, we for the first time report the evaluation of protonic conductivity in BaZr1-xCexY0.2O3−δ (BZCY) and BaZr0.1Ce0.7Y0.2–xYbxO3–δ (BZCYYb) by direct measurements afforded by the Isotope Exchange Depth Profiling (IEDP) technique with deuterium labelling. We also report the kinetics of H/D transport through the bulk materials and across metal-ceramic interfaces with particular interest in the behaviour of the interface between the key Pd/Pd alloy catalyst component and the hydrogen transporting oxide ceramic material. The transport and interface behaviour information will be of significance in designing hydrogen separation and compression membranes.