Given the fact that polycrystalline SrZrO3 doped with 5 mol% Y3+ (p-SZY5), a proton-conducting solid electrolyte with superior chemical stability, has attracted considerable attention over the past years due to its potential for various applications including hydrogen pumps, it is rather unusual that such little information is available in literature regarding the electrical nature of the grain boundary in this material, although the grain boundary may determine its proton conductivity. Here we report the results of our investigation on the conduction mechanism at the grain boundary in p-SZY5. We clearly demonstrate that the current-voltage (I-V) characteristic of the grain boundary is consistent with thermionic emission current over a back-to-back Schottky barrier, suggesting that such a potential barrier is present at the grain boundary in p-SZY5 to limit the internal proton current. More importantly, based on the capacitance-voltage relation, we were able to deduce the values of both the potential-barrier height and the dopant concentration in p-SZY5. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.