Because of their high ionic conduction even at relatively low temperatures, proton conducting ceramics are one of the most promising electrolytes for fuel cell. In contrast to oxide-ion conductors, proton-conducting systems, especially in an electrolyser plant, could operate below 600 degrees C, critical temperature for mechanical and hot corrosion resistance of common stainless steels. Proton conduction in perovskite type ceramic was analysed under the water molecules insertion to maximize proton conduction. To this end, the SrZr(0.9)Ln(0.1)O(2.95) electrolyte and its microstructure, particularly grain size was investigated. The insertion and release of water in the perovskite structure was followed by impedance spectroscopy and by using the so-called Brick Layer Model (BLM) to separate the bulk and grain boundary conductivities. It was found that the conductivity in both zones increases namely with steam pressure. It was also verified that the bulk conductivity is higher than that of grain boundaries. Consequently both the operating steam pressure and the grain size appear as the main parameters that can be tuned to enhance the proton conduction. (C) 2014 Elsevier B.V. All rights reserved.