Abstract This chapter describes the structure of electrode/solution interfaces and the origin of the electrode potential. Equilibrium conditions are considered. The energy of particles in a phase, the equilibrium between phases and the origin and the physical significance of electrode potentials are discussed. Two main systems are considered: metal/solution and oxide/solution interfaces. Potential of zero charge for the former and point of zero charge for the latter are defined. The structure of the interface and its dependence on a number of parameters such as electrode potential, crystallographic orientation, nature of the solid, etc. are discussed. The fundamental importance of the interaction between the solid and the solvent and its influence on adsorption phenomena is stressed.