The nature and composition of the Fe minerals in the rusty ferruginous material frequently located in the zone of contact between the thallus of Stereocaulon vesuvianum and the leucite bearing rock of Mt. Vesuvius have been studied by microscopic and submicroscopic investigations (SEM, TEM with EDXRA) complemented by X-ray diffraction and chemical analysis. Ferrihydrite is likely to be the main component of the short-range order iron oxyhydroxide pool, although the possibility that significant feroxyhite may be present cannot be completely excluded. Hematite and goethite are the crystalline iron oxides. The organic acids produced by lichens play a key role in the enrichment of poorly-ordered phases at the rock-lichen interface. It is suggested that the peculiar morphology of the Stereocaulon vesuvianum thallus and the irregularity of the volcanic rock surface lead to different microsites in the rock-lichen interfaces which have their own conditions of pH, humidity and redox potential, favourable for the neoformation of crystalline phases.