The chemistry of S‐donor ligands with metal centres is reviewed with emphasis placed on the structures and redox activity of the resultant complexes. Sulfides and thiolates bind to a wide range of metal ions. The oxidation of thiolates to sulfones and sulfoxides and the structures and chemistry of metal‐thiolene complexes are detailed. Thioethers are generally poor ligands for transition metal ions but macrocylic ligands afford stable complexes. Many metalloproteins contain metal–sulfur bonds and the structures of many of these have now been elucidated. This has sparked a renaissance in the synthesis of low‐molecular weight metal complex mimics.