Abstract Incorporation of “green chemistry” principles into nanotechnology has become one of the key subjects for nanoscience researches. In this work, we report an electrochemical reaction with ECE mechanism on the surface of 1,2,4-triazole-3-thiol-protected silver nanoparticles (TATAgNPs) via electrochemical oxidation of catechol in the presence of TATAgNPs. The reaction proceeds via the nucleophilic 1,4-Michael addition of TATAgNPs to electrochemically generated o -benzoquinone in aqueous solution and at ambient temperature and pressure. The occurrence of ECE mechanism on the Ag nanoparticles was proved by cyclic voltammetric and controlled potential coulometry. Also functionalized AgNPs were characterized by UV–Vis spectroscopy, dynamic light scattering (DLS) and transmission electron microscopy (TEM) techniques.