The present manuscript showcases studies of the interaction of organic and inorganic ligands (adsorbates) with mono-metallic noble-metal electrocatalysts that have helped establish the surface coordination chemistry of these materials in aqueous solutions; experimental measurements were based upon electrochemical and surface analytical techniques. The most important trend observed from such studies is that the chemisorptive properties of the noble metal electrodes follow the molecular organometallic or coordination chemistry of these metals; that is, it is possible to model surface compounds in terms of homogeneous monometal or cluster complexes.