Potassium-rich ash-based glass is typical of medieval glass windows used in the Central Europe since 1000 A. D.. Glasses with medieval-like composition were prepared with different amounts of K2O (15–20–25 K2O weight%) using recipes deduced from archaeometric literature. Raman data of these samples were interpreted on the basis of the Qn units model and of the polymerization index Ip and confirm a close dependence of glass depolymerization on the potassium content. Generally, K-based glasses have high alteration sensitivity to pollutants conveyed by liquid or vapour water (rain, humidity and fog). In this work, the glass alteration processes were studied in terms of structural modifications related to the glass K content. Leaching and network dissolution were investigated by attack with boiling concentrated sulfuric acid and by exposure to high temperature and high pressure bidistilled water, respectively. The weight loss and alteration layer thickness were measured. The structural changes in the glass network and the presence of neoformation crystallized products were determined through linear Raman maps on altered glass cross sections. The more the glass network structure is depolymerized, the more the surface chemical attack is facilitated. The results obtained for the model glasses are compared with those for a set of ancient K-rich glass fragments. Copyright © 2012 John Wiley & Sons, Ltd.