The abundances of the stable isotopes of the bioelements are not constant. Subtle, but significant, variations may be induced by physical, physiological and biochemical processes. These variations may be detected and quantified. Often, isotope fingerprints are characteristic of certain processes and may reveal information concerning the sources and origins of compounds of interest. Moreover, natural variabilities of stable isotopes may be exploited in order to perform tracer experiments. The most accurate technology to perform stable isotope analysis is (gas) isotope ratio MS (IRMS). Compound-specific approaches employ hyphenation of GC and LC to IRMS. In these approaches, complete conversion to simple gases prior to MS is required. Analysis by stable isotope ratio spectroscopy currently approaches the accuracy of IRMS. However, for bioanalytical projects, it is still predominantly confined to material synthetically enriched with stable isotopes.