The electrochemical activity of thermo-decomposed Ti/IrO2 electrodes in aqueous solution containing methanol compound has been studied, emphasizing on the influence of calcination temperature. Scanning electron microscopy (SEM) images showed that the typical cracked morphology of oxide coatings disappears gradually as the preparation temperature increases, leading to the decrease in the amount of electrochemically active sites as measured by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in organics-free aqueous solution. With the exception of samples prepared at high temperatures (e.g. 600 degrees C), same change tendency of electro-activity with temperature was also found in methanol aqueous solutions, in which activity was observed to decrease as compared with that in blank solution. Three possible explanations for this phenomenon (i.e. active dissolution of oxide coatings, organics adsorption and dimerization/polymerization on electrode surface, respectively) were discussed, where the former two were believed to be more reasonable considering the CH3OH small molecular chosen in this system. However, none of these three mechanisms could explain the abnormal activation behavior observed at electrodes prepared at 600 degrees C in CH3OH solution. XRD pattern showed the fact that when sintering temperature went up to 600 degrees C IrO2 would decompose into metallic iridium component. The existence of metallic iridium might facilitate the organics oxidation as stated in previous literatures, which leads to the exceptional activation of oxide surface by methanol component. A simple reaction mechanism for electrodes in methanol aqueous solutions was proposed and used to interpret the negative shift in startness potential of the oxygen evolution reaction (OER). Organics oxidation seems to facilitate the OER and vice versa. The latter statement has been reported by other workers. (c) 2006 Elsevier Ltd. All rights reserved.