Ruthenium oxide catalysts were prepared by a sol gel technique and calcined at different temperatures e.g., 400 degrees C, 500 degrees C and 600 degrees C. The catalysts performance for the oxygen evolution reaction was studied using cyclic voltammetry and their performance in a high temperature proton exchange membrane water electrolyser (PEMWE) examined. Physiochemical characterization was carried out to study the thermal stability, oxygen-metal bond formation, crystallinity phase and crystallite size, particle size and elemental analysis by TGA, FTIR, XRD, TEM and EDX respectively. The electrolyte used for electrochemical characterisation was 1.0 M H3PO4 and 0.5 M H2SO4. Additionally, the effect of calcination and electrolyte temperature on oxygen evolution reaction of RuO2 catalysts was studied and the apparent activation energy was determined using chronoamperometry. The prepared RuO2 were tested as anode catalyst in PEMWE in the temperature range of 120-150 degrees C using phosphoric acid doped polybenzimidazole membrane electrolyte. The physio-chemical and electrochemical characterization results indicate that RuO2 calcined at 500 degrees C gave the best performance with a current density of 0.875 A cm(-2) at 1.8 V in a PEMWE operated at 150 degrees C. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.