The preparation, characterization and analytical applications of gold electrodes modified with ω-mercapto alkyl/aryl sulfonates are described. The devices resulted effective for the determination of free and labile Pb(II) in water samples by anodic stripping voltammetry (E dep =−600mV) and in particular 2-mercaptobenzimidazole-5-sulfonate (MBIS) offered the best performances with detection limit of 0.4μgL −1 .Quantitative stripping of Pb from the electrode surface during the anodic scan, is obtained using sodium citrate buffer (pH=9.0) as supporting electrolyte. Natural waters were analysed by standard addition method with good recoveries (mean percentage=97%); no fouling effects due to humic acids or other organic constituents were observed in the reported conditions.