The adsorption of alkali metals on graphite has been the subject of various studies for the
past two decades. Briefly, two main reasons can be offered to justify the persisting interest
in these adsorption systems. First, experiments have pointed out intriguing structural
phase transitions of the adsorbed species, and, second, in an attempt to explain the
experimental results, the more complicated question of the nature of alkali metal–graphite
bonding arose. Despite the relative simplicity of the electronic structure of the alkali
metals, their interaction with the graphite surface is still the subject of current debate.
This review paper presents relevant experimental data and results of selected
theoretical calculations that, in time, guided the process of scientific discovery
towards the current understanding of the alkali metals/graphite adsorption systems.