An experimental illustration of the formation of a band structure in a solid is presented. It is based on the structure analysis of the x‐ray excited photoelectron valence band spectra recorded for a series of molecules with increasing length, the linear normal‐alkanes (CnH2n+2, where 1≤n≤∞). This experiment shows how a single atomic carbon 2selectronic level evolves to molecular orbitals, and then to a band, as the numbernof carbon atoms increases in the molecule and simulates at the end a 1‐D solid. It is thought that such a simple picture might help to understand and illustrate a solid state physics course about band structures.