Interference from selenium affects the electrochemical determination of tellurium due to their overlapped redox potentials. Benzenedithiols (BDT) self-assembled monolayers (SAMs) modified gold electrodes were investigated in this study to determine Te(IV) in the presence of Se(IV). The microenvironment from SAMs of benzenedithiols on the gold surface allows for extraction of Te(IV) selectively over Se(IV). By suppressing the reduction of Se(IV), it provides an approach to determinate Te(IV) in the presence of Se(IV) with potential applications for biological membrane, membrane techniques and geochemistry analysis. Published by Elsevier Ltd.