A 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate (AHMP)-based self-assembled monolayer (SAM) was formed on the gold electrode surface. Ellipsometric measurements evidenced the SAM formation on the gold electrode surface. The structural integrity of the modified gold electrode was also characterized by insulating properties of the SAM that were detected by cyclic voltammetry. The results of cyclic voltammetry showed that the SAM, which was formed by assembly of AHMP, was stable but did not completely block the redox-activity of ferrocene and K3[Fe(CN)6]/K 4[Fe(CN)6]. In contrast completely blocked redox-activity was observed after the treatment of AHMP-based SAM with saturated solution of 4-formylphenylboronic acid in 1,4-dioxan. The modified electrodes exhibited a selective response towards Cu(II) ions in the presence of some interfering ions such as Cd(II), Co(II), Fe(II), Ni(II) and Pb(II). This study is the first scientific report on the application of AHMP-modified electrode as a selective Cu(II) sensor in the presence of some interfering cations. © 2011 Elsevier B.V. All rights reserved.