Ionic liquids (ILs) have become an established option for the use as electrolytes in dye‐sensitized solar cells. In the present study, the adsorption of a multitude of different ILs on a TiO2 surface is studied systematically, focusing on the energetic modifications of the semiconductor. The cation was found to generally cause an energetic downward shift of the TiO2 band levels by accepting electron density from the surface, and the anions were observed to function in the opposite direction, raising the energy levels by donating electron density. Both effects counterbalance each other, leaving the desired outcome dependent on the choice of the specific IL, i.e., the choice of the cation/anion combination. The correlation of the band levels with the properties of the IL was successfully achieved. The dipole moment of the adsorbed ionic liquid species showed little to no correlation with the semiconductor energetics, but the charge transfer calculated by radical Voronoi tessellation revealed a high correlation. The current findings contribute to a deeper understanding of the role of the electrolyte in dye‐sensitized solar cells, and ILs in general, and help with choosing and tuning of the electrolyte solutions in existing applications. The electrolyte effect! The adsorption of cations and anions from ionic liquids is decisive for the band level alignment in dye‐sensitized solar cells. Electron deficiency typically caused by cations results in an energetic lowering of states, that is, valence and conduction bands. Consequently, electron donation from anions results in an energetic increase of states.