The most important mercury species in the environment is monomethylmercury (MMHg), the topic of this chapter. This organic mercury compound is normally not released into the environment but formed by natural processes. Mercuric mercury (Hg²(+)) is methylated by bacteria and to a lesser extent through abiotic pathways. Highest rates of formation are found in anoxic aquatic environments. Terrestrial systems are mostly irrelevant for MMHg production and not a concern. Most productive environments are sediments, wetlands, and coastal marshes, but also the anoxic hypolimnion of lakes and anaerobic microhabitats like the rhizosphere of floating macrophytes. Prime suspects for methylation are sulfate-reducing bacteria, although also iron reducers have lately been identified as capable mercury methylators. What makes methylmercury such an insidious contaminant is its enormous biomagnification potential. Methylmercury is accumulated by more than seven orders of magnitude from sub ng/L concentrations in water to over 1,000,000 ng/kg in piscivorous fish, which are the main concern from a human health point of view. Since methylmercury is a very potent neurotoxin, particularly small children, pregnant women, and women in childbearing age are advised to either limit their fish consumption to a few meals per week or to select fish species known to have low levels of methylmercury. Formation of methylmercury is counteracted by other bacteria, which are capable of demethylating methylmercury. This process is regulated by an inducible mer operon system and serves as a detoxification mechanism in polluted environments. The other naturally occurring organic mercury species, dimethylmercury (DMHg), is only present at very low levels at great depths in the world oceans. However, it might be an important and very mobile pre-cursor for methylmercury in marine and polar ecosystems.