Classical electrochemical and microscopy methods were used to characterize the interfacial processes of the adsorption of chloride ions from ionic liquids at the Bi(111) single crystal electrode. The mixture of 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium chloride was electrochemically characterized by using cyclic voltammetry and electrochemical impedance spectroscopy. In situ scanning tunneling microscopy images showed the formation of superstructures at the electrode’s surface over an extended period of time. The specific adsorption of chloride ions reaches an equilibrium state in a more viscous ionic liquid medium slower than in aqueous and organic solvents. Capacitance values increase considerably (also depending on alternative current frequency) at the potential region, where the specific adsorption of chloride ions with partial charge transfer occurs.