The structure of the interfacial layer(s) between the extremely pure air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate and Au(111) has been investigated using in situ scanning tunneling microscopy (STM) at electrode potentials more positive than the open circuit potential. The in situ STM measurements show that layers/islands form with increasing electrode potential. According to recently published atomic force microscopy (AFM) data the anion is adsorbed even at low anodic overvoltages and adsorption becomes slightly stronger with increasing electrode potential. Furthermore, the number of interfacial layers increases with increasing electrode potential. The present discussion paper shows that these layers are not uniform and have a structure on the nanoscale, supporting earlier results that the interface electrode/ionic liquid is highly complex. It is also shown that the addition of solutes changes this structure considerably. AFM results reveal that in the pure liquid, interfacial layers lead to a repulsive force but the addition of 10 wt% of LiCl leads to an attractive force close to the surface. These preliminary results show that solutes strongly alter the interfacial structure of the ionic liquid/ electrode interface.