In this article, within an ab initio density functional framework, we study the charge rearrangement in chemisorption of an isolated atom on a simple metal surface described by jellium. We focus our attention on the electron localization function (ELF) and illustrate how this function can complement the total charge density contour plots for the understanding of chemisorption. The ELF of Li, Cl, Si, and Fe adatoms are discussed. In all such cases the ELF shows itself as a wealthier, more immediate and visually informative pattern of the charge rearrangement. By varying the atom-surface distance of Fe, the formation of the chemisorption bond and the role played by the majority and the minority spin populations are discussed.