The study of heterodentate molecules adsorbed on metal electrodes provides an opportunity to expand the functionality of modified surfaces while offering insights into the surface and intramolecular electronic interactions of organic adsorbates. The adsorption of 2-(2'-thienyl)pyridine, a molecule containing both pyridine and thiophene moieties, on a Au(111) electrode is reported. Adsorption was characterized by electrochemistry in neutral and basic aqueous electrolyte and was compared to that of pyridine. The aqueous electrochemistry of thiophene on Au(111) was also characterized for comparison purposes. At negative potentials, in the presence of 2-(2'-thienyl)pyridine, a diffuse, pi-bonded monolayer was formed, and a phase transition to a close-packed N- and/or S-bonded configuration was observed near -0.4 V in a 1 mM solution of adsorbate, similar to that seen in pyridine on Au(111). The thiophene-like oxidative dimerization of the molecule was confirmed at positive potentials using in situ fluorescence microscopy by comparison with the spectrum of the chemically synthesized dimer.