By using a radioactive labeling method and electrochemistry, results were obtained that show that interactions of bisulfate anion with well‐ordered single‐crystal electrodes are different from those with the polycrystalline electrodes. In particular, the anion surface concentration on the polycrystalline rhodium electrode increases monotonically with the electrode potential and then decreases when the surface becomes electrooxidized. With Rh(111), the surface stability of bisulfate is observed in a broad electrode potential range. Likewise, the hydrogen adsorption process apparently overcomes a higher energy barrier to nucleate into surface water‐bisulfate network on Rh(111) than it does on the polycrystalline surface. These findings, and the corresponding results obtained with platinum electrodes, demonstrate some unique electrochemical properties of electrode materials that have a regular atomic periodicity and a long‐range crystallographic order. Extension of this work to surfaces covered by underpotential‐deposited‐metal (UPD) adlayers illustrates the principles of “enhanced” adsorption.4 That is, the anionic adsorption from solutions containing cationic UPD precursors is observed in the potential range where no anion adsorption occurs on the clean substrate surfaces. It is shown here for the first time that there are some inactive and active UPD metal adlayers toward adsorption. In the case of adsorption of bisulfate on platinum covered by UPD copper, it is concluded that in the inactive electrode potential range perchlorate successfully competes with bisulfate for the surface sites. This observation is easy to embrace if the UPD copper adlayer is composed of Cu1+ cations41 rather than neutral copper adatoms. In general, it is demonstrated that a simple electrostatic approach to the anion bonding with metal electrodes is not appropriate. There is a chemical component involved in adsorption that merits further investigation.