The adsorption and reactivity of cyanate at Au(111) single crystal and Au(111)-25 nm thin film electrodes is studied spectroelectrochemically in sodium perchlorate solutions and compared to those of cyanuric acid (C3N3O3H3). From the Surface Enhanced Infrared Reflection Absorption spectra obtained under Attenuated Total Reflection conditions (ATR-SEIRAS) it can be concluded that adsorbed cyanate species predominate at the electrode surface for low cyanate concentrations. However, for cyanate concentrations above 1 mM, the similarity of the ATR-SEIRA spectra with those obtained in cyanuric acid containing solutions indicates that some species coming from cyanuric acid is formed and adsorbed at the (111) gold surface sites as the result of an electroless trimerization reaction. Taking into account the results of Density Functional Theory (DFT) calculations, the experimental voltammetric and ATR-SEIRAS results agree with the formation of adlayers of specifically adsorbed triketo-monocyanurate species that adsorb perpendicular to the electrode surface. (C) 2017 Elsevier B.V. All rights reserved.