The chemical and ultrastructural features of the interface formed by different biotypes of saxicolous lichen species with their rock substrata were investigated in the semiarid habitat of the SE Iberian Peninsula and the relationships between the bioweathering patterns observed and lichen colonization selectivity towards the different rock substrata evaluated. Xanthoria parietina was able to fix to the rock substratum by the adherence of single cell walls from the lower cortex. Neofuscelia pulla used rhizines and loose groups of hyphae for attachment of the thallus to the rock. Colonization by the foliose lichen species was confined to the rock surface, while Diploschistes diacapsis was also able grow below the surface showing two types of hyphal growth. Minerals in close contact with cell walls were biochemically and biophysically weathered, but hyphae showing calcium oxalate crystals did not appear to be directly involved in the patterns observed. The textural characteristics of the substratum seemed to be related to the type of microorganism colonization: sedimentary rocks were more deeply colonized by lichens and other chasmolithic microorganisms than volcanic material. Calcium oxalate crystals were found in the medulla of N. pulla but not at the lichen-substratum interface. Crustose lichens such as D. diacapsis showed calcium oxalate crystals in the upper cortex and over the outside of fungal medullary hyphae but not in direct contact with the rock surface. Calcium oxalate precipitation seems to be related to the different metabolic activities of the mycobiont within the lichen thallus and to different species. D. diacapsis inhibits the growth of other microorganisms in close proximity to the thallus, whereas foliose species were associated with several communities of microorganisms.