My book presents the applications of X-ray absorption spectroscopy (XAS) to the study of cobalamines, a family of organometallic molecules that play an essential role in the metabolism of all living things. I carried out several experiments on synthetic or biological samples, using different variants of XAS, such as XANES or EXAFS. I also used theoretical and numerical tools to interpret my data and compare them with those in the literature.In my book, I invite you to discover :- The base-off/base-on reaction of cobalamines, which modifies the geometry and stability of cobalamines.- The interaction between haptocorrin and cobalamins, which involves a modification of cobalt coordination and protection against oxidation.- The photolysis reaction of alkylcobalamines, leading to the disruption of the cobalt-carbon bond and the formation of a free radical.- Synthesis and characterization of cobaloximes, "model compounds of vitamin B12".- The interaction between glutathione and cobalamins, leading to the formation of glutathione-cobalamin complexes.