Garlic has long been considered as a natural remedy against a range of human illnesses, including various bacterial, viral and fungal infections. This kind of antibiotic activity of garlic has mostly been associated with the thiosulfinate allicin. Even so, recent studies have pointed towards a significant biological activity of trisulfides and tetrasulfides found in various Allium species, including a wide range of antibiotic properties and the ability of polysulfides to cause the death of certain cancer cells. The chemistry underlying the biological activity of these polysulfides is currently emerging. It seems to include a combination of several distinct transformations, such as oxidation reactions, superoxide radical and peroxide generation, decomposition with release of highly electrophilic S(x) species, inhibition of metalloenzymes, disturbance of metal homeostasis and membrane integrity and interference with different cellular signalling pathways. Further research in this area is required to provide a better understanding of polysulfide reactions within a biochemical context. This knowledge may ultimately form the basis for the development of 'green' antibiotics, fungicides and possibly anticancer agents with dramatically reduced side effects in humans.