Iridium oxide (IrOx) films formed electrochemically on the surface boron doped diamond electrode by potential cycling in the range −0.2 to 1.2V from a saturated solution of alkaline iridium(III) solution. A strongly adherent deposit of iridium oxide is formed after 5–10 potential scans. The properties, stability and electrochemical behavior of iridium oxide layers were investigated by atomic force microscopy and cyclic voltammetry. The boron doped diamond (BDD) electrode modified with electrodeposition of a thin film, exhibited an excellent catalytic activity for oxidation of Hg(I) over a wide pH range. The modified electrode shows excellent analytical performance for Hg(I) amperometric detection. The detection limit, sensitivity, response time and dynamic concentration ranges are 3.2 nM, 77 nA M−1, 100 ms and 5 nM–5M. These analytical parameters compare favorably with those obtained with modern analytical techniques and recently published electrochemical methods. © 2005 Elsevier B.V. All rights reserved.