The analytical studies carried out during two different diagnostic surveys, respectively in 1983 and 2003, offered the opportunity to control decay phenomena development on stones facing Certosa of Pavia (Italy). Calcium oxalate films and red stains, present on Carrara marble surface, have been particularly focused; these are the only decay phenomena which apparently have remained unchanged during a period of twenty years. More sensitive and in-depth analytical studies (FTIR equipped with diamond cell, GC-MS, SEM-EDS and optical microscopy) achieved a better knowledge about their composition. Results allowed a critical evaluation of the role of oxalate films on the external marble surface and to suggest new hypotheses about the formation of red stains.