Electron microscopic characterisation of 7-year old alkali-activated blast-furnace slag concretes enabled the identification of distinct microstructural features, providing insight into the mechanisms by which these materials evolve over time. Backscattered electron images show the formation of Liesegang-type ring formations, suggesting that the reaction at advanced age is likely to follow an Oswald supersaturation–nucleation–depletion cycle. Segregation of Ca-rich veins, related to the formation of Ca(OH)2, is observed in microcracked regions due to the ongoing reaction between the pore solution and available calcium from remnant slag grains. A highly dense and uniform interfacial transition zone is identified between siliceous aggregate particles and the alkali activated slag binders, across the concretes assessed. Alkali-activated slag concretes retain a highly dense and stable microstructure at advanced ages, where any microcracks induced at early ages seem to be partially closing, and the remnant slag grains continue reacting.