The spinel-type Co3O4 films have been prepared on a conductive support using a sol-gel route at 350degreesC and their physicochemical and electrochemical properties towards O-2-evolution in alkaline solutions using TGA/DTG, IR, XRD, SEM, conductivity, CV, impedance and Tafel polarization techniques were investigated. The results showed that the nature of the precursor influenced the roughness factor as well as the electrocatalytic activity of the oxide films for O-2-evolution greatly. The ratio of molar concentrations of precursors (i.e. x = [CoSO4]/[LiOH]) also strongly influenced the electrocatalytic properties of the catalyst. The electrocatalytic activity in 1 M KOH was observed to be maximum for the catalytic film obtained at 0.67 less than or equal to x less than or equal to 1.33. The Tafel slope and the reaction order found on the active catalytic films were 50-56 mV decade(-1) and 1.1-1.5, respectively. The activation energy of the reaction was observed to be approximately constant (47.8 +/- 0.6 kJ mol(-1)) at low potentials (0.58 and 0.60 V) only. This electrode has shown a good performance up to the observed current density of 1.0 A cm(-2) in 30 wt% KOH even at 70degreesC. (C) 2002 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.