Capacitive energy storage devices are receiving increasing experimental and theoretical attention due to their enormous potential for energy applications. Current research in this field is focused on the improvement of both the energy and the power density of supercapacitors by optimizing the nanostructure of porous electrodes and the chemical structure/composition of the electrolytes. However, the understanding of the underlying correlations and the mechanisms of electric double layer formation near charged surfaces and inside nanoporous electrodes is complicated by the complex interplay of several molecular scale phenomena. This Perspective presents several aspects regarding the experimental and theoretical research in the field, discusses the current atomistic and molecular scale understanding of the mechanisms of energy and charge storage, and provides a brief outlook to the future developments and applications of these devices.