The recognition of extinct or extant life signatures in the terrestrial geological record is fundamentally dependent upon the understanding of both the structural morphology and chemical composition of relict biomaterials; the identification of cyanobacterial colonies that have adapted biogeologically their mineral matrices in early evolutionary processes is a fundamental step in the acquisition of analytical data from remote planetary probes designed for life-detection experiments, particularly on Mars and on the planetary satellite moons, Europa and Titan. A key factor in the assessment of early life signatures is the molecular presence of chemicals designed to protect the emerging organisms from the damaging effect of radiation exposure and of desiccation and temperature changes; in this respect the non-destructive capability of Raman spectroscopy to delineate the interfacial interactions between substrates and endolithic biology is now deemed an essential part of the ExoMars life-detection suite of instrumentation planned by the European Space Agency in the AURORA programme. A description of the scientific basis for the biogeological discrimination offered by Raman spectroscopy between organic and inorganic moieties in specimens from terrestrial Mars analogue sites is followed by selected examples of the type of analytical information provided, which will be complementary to the elementary and microscopic data obtained from other instrumentation on the same mission.