This paper presents the investigation of the activity of silver electrode treated by cyclic voltammetric (CV) method with H2O2 + KI in aqueous solution on the oxidation of NaBH4. Among the various treatment solutions investigated, H2O2 + KI solution shows the best performance with the maximum catalytic activity. CV treatment in H2O2 + KI on Ag electrode improves the catalytic activity more than bulk electrolysis (BE) due to increase in surface porosity. Apart from the catalytic effect of this surface in the oxidation of BH4- it was also observed that there is a formation of hydrolysis product of BH3OH- of BH4- during the anodic scan between -0.25 and -0.45 V which is seen to be converted back to BH4- during the cathodic scan. (C) 2010 Elsevier B.V. All rights reserved.