In this work, the interfacial nanostructure and electrowetting of ionic liquids having the same 1-ethyl-3-methylimidazolium cation ([EMIm]) but different anions such as bis(trifluoromethylsulfonyl)imide (TFSI-), trifluoro-methylsiilfonate (TfO-), methylsulfonate (OMs-), acetate (OAC(-)), bis(fluorosulfonyl)imide dicyanamide (DCA(-)), and tris(pentafluorethyl)trifluorphosphat (FAP(-)) on bare metallic electrodes were investigated. In the investigated voltamrnetric potential regime, the contact angle versus voltage curve is asymmetric with respect to surface polarity. The electrowetting of the ILs occurs at negative potentials but does not occur at positive potentials. In situ atomic force microscopy (AFM) shows that the IL adopts a multilayered structure at the solid/IL interface, and a cation-rich layer is present in the innermost layer during cathodic polarization. The cations can change their orientation and propagate ahead of the threephase contact line by diffusion, leading to further spreading on the negatively charged surface. The formation of such a surface layer is also evidenced by X-ray photoelectron spectroscopy. Such a surface diffusion mechanism does not occur during anodic polarization; where anions are enriched. In addition, the influence of substrate, water, and dissolved zinc salts on the electrowetting of ILs was studied. Our findings provide valuable insights for the interfacial nanostructure and the electrowetting of ILs.