Adsorption of ions and hydrophobic molecules are ubiquitous and vital processes at electrochemical interfaces, which regulate the molecular composition of the interface and the chemistry therein. They are dictated by a subtle balance of free energy contributions from electrostatics, solute–surface interactions, and solvation. In this chapter, we target the most elusive solvation contributions. We review some recent progresses that have been made by developing advanced vibrational spectroscopy, with emphasis in the low frequency THz range, and computational techniques. We discuss some of the exciting perspectives that tuning hydrophobicity and solvation properties of metal-aqueous interfaces opens for the optimization of several electrochemical processes.