Sulfur has been known since antiquity, and oxygen was recognized as an element in the 18th century. Selenium, tellurium and polonium were discovered in the 19th century, and livermorium in 2000. All of the chalcogens have six valence electrons, leaving them two electrons short of a full outer shell. Their most common oxidation states are −2, +2, +4, and +6. They have relatively low atomic radii, especially the lighter ones.

Lighter chalcogens are typically nontoxic in their elemental form, and are often critical to life, while the heavier chalcogens are typically toxic. All of the chalcogens have some role in biological functions, either as a nutrient or a toxin. The lighter chalcogens, such as oxygen and sulfur, are rarely toxic and usually helpful in their pure form.[citation needed] Selenium is an important nutrient but is also commonly toxic. Tellurium often has unpleasant effects (although some organisms can use it), and polonium is always extremely harmful, both in its chemical toxicity and its radioactivity.

Sulfur has more than 20 allotropes, oxygen has nine, selenium has at least five, polonium has two, and only one crystal structure of tellurium has so far been discovered. There are numerous organic chalcogen compounds. Not counting oxygen, organic sulfur compounds are generally the most common, followed by organic selenium compounds and organic tellurium compounds. This trend also occurs with chalcogen pnictides and compounds containing chalcogens and carbon group elements.

Oxygen is generally extracted from air and sulfur is extracted from oil and natural gas. Selenium and tellurium are produced as byproducts of copper refining. Polonium and livermorium are most available in particle accelerators. The primary use of elemental oxygen is in steelmaking. Sulfur is mostly converted into sulfuric acid, which is heavily used in the chemical industry. Selenium's most common application is glassmaking. Tellurium compounds are mostly used in optical disks, electronic devices, and solar cells. Some of polonium's applications are due to its radioactivity.