The rapid and reversible ionic electrosorption in the electrical double layers (EDLs) of moderately charged micropores in contact with a solution is the main concept underlying capacitive energy and desalination devices. For the usual operating conditions, the ion concentration is large enough for the confinement of ions to play an important role in their distribution in the EDL. On the other hand, although most laboratory experiments have been carried out with simple salt solutions, realistic applications require a proper analysis of the effect of the different ionic species existing in natural waters. Here we focus on the role of multiionic solutions on the double layer structure. For this purpose, a model is presented in which the EDL overlap and the existence of a Stern layer are considered. It is also taken into account that the ions can be tightly packed by using the Carnahan–Starling model. This model is applied to analyze the structure of the EDL with multiionic solutions containing divalent ions. The predictions of this model are found to largely differ from those of the better known Bikerman equation, and are more realistic. It is demonstrated that the presence of tiny amounts of divalent ions in the bulk is enough to dominate the EDL behavior, and hence, its capacitance, energy storage, and desalination properties.