Understanding the composition evolution of grain boundaries and grain boundary precipitation at near-atomic scale in aluminum alloys is crucial to tailor mechanical properties and to increase resistance to corrosion and stress corrosion cracking. Here, we elucidate the sequence of precipitation on grain boundaries in comparison to the bulk in a model Al-Zn-Mg-Cu alloy. We investigate the material from the solution heat treated state (475°C), through the very early stages of aging to the peak aged state at 120°C and further into the overaged regime at 180°C. The process starts with solute enrichment on grain boundaries due to equilibrium segregation accompanied by solute depletion in their vicinity, the formation of Guinier–Preston (GP) zones in the solute-enriched grain boundary regions, and GP zones growth and transformation. The equilibrium segregation of solutes to grain boundaries during aging accelerates this sequence compared to the bulk. Analysis of the ~10 nm wide precipitate-free zones (PFZs) adjacent to the solute-enriched grain boundaries 2 shows that the depletion zones are determined by (i) interface equilibrium segregation; (ii) formation and coarsening of the grain boundary precipitates and (iii) the diffusion range of solutes in the matrix. In addition, we quantify the difference in kinetics between grain boundary and bulk precipitation. The precipitation kinetics, as observed in terms of volume fraction, average radius, and number density, is almost identical next to the depletion zone in the bulk and far inside the bulk grain remote from any grain boundary influence. This observation shows that the region influenced by the grain boundaries does not extend beyond the PFZs.