A unique property of sulfur is the ability to form chains of sulfur atoms with organic groups at either end—e.g., RS_nR′, where n can range from 2 to 20 or more. They are named by designating, in alphabetical order, the groups attached to sulfur, followed by the word sulfide, which is preceded by the prefix appropriate to the number of sulfur atoms, as in disulfide, trisulfide, tetrasulfide, and so forth or by use of dithio-, as in dithiodiacetic acid. Polysulfides are also named polysulfanes, with individual compounds being named trisulfane, tetrasulfane, and so on. A variety of disulfides occur in nature. The amino acid cystine, a disulfide, is an important component of many proteins; the sulfur-sulfur bond plays a key role in maintaining the molecules in shapes (so-called tertiary structures) essential for their biological activity. Interconversion of cysteine sulfhydryl (―SH) and cystine disulfide groups plays an important role in transport across cell membranes, in the immune process, and in blood clotting. The process of hair waving involves cleavage of the cystine disulfide link of keratine into the cysteine moiety, providing flexibility for the hair to assume the new wave or curl desired, followed by oxidative treatment to fix the hair in its new shape.

The coenzyme lipoic acid, a cyclic disulfide, is a growth factor—ubiquitously distributed in plants, animals, and microorganisms—and is used in photosynthesis and lipid and carbohydrate metabolism in plants and animals. It is involved in biological oxidations, where it oscillates between the oxidized cyclic form and the reduced acyclic dithiol form. Lipoic acid suffers from ring strain caused by repulsion of lone-pair electrons on adjacent sulfurs in the near planar ring, making it a better oxidizing agent than a six-membered cyclic disulfide, such as 1,2-dithiane, would be. At the same time, in the reduced dithiol form, the thiol groups are in sufficient proximity to facilitate reoxidation. Asparagusic acid (4-carboxy-1,2-dithiolane), found in asparagus roots, is considered to be a major factor in the natural resistance (i.e., survival in the soil) of this plant; 4-methylthio-1,2-dithiolane is a photosynthesis inhibitor from the stonewort. The characteristic flavour of the shiitake mushroom is due to the presence of the acyclic disulfide-sulfone CH₃SO₂CH₂SCH₂SCH₂SSCH₃ together with several cyclic polysulfides, including lenthionine; thiarubrine is a novel biologically active acetylenic cyclic disulfide found in plants related to marigolds. Dimethyl trisulfide (CH₃SSSCH₃), detectable at levels as low as 0.1 part per billion, is a key contributor to the flavour of beer, wine, whiskey, and various food products. It is also one of a number of organosulfur compounds present in coal.

When garlic cloves are distilled with water, garlic oil is isolated and is found to contain a mixture of compounds including diallyl disulfide, trisulfide, and polysulfides—e.g., (CH₂=CHCH₂)₂S_n, where n = 2–8. None of these compounds occur naturally in garlic; rather, they are formed from the action of water and heat on allicin, a biologically active thiosulfinate, or disulfide S-oxide, CH₂=CHCH₂S(=O)SCH₂CH=CH₂, in turn formed enzymatically from sulfoxide precursors in the intact garlic bulb (see below Sulfoxides and sulfones: Reactions). Sulfurized olefins are used in extreme pressure lubrication, while a highly resistant sulfur cement and concrete can be prepared from cyclopentadiene Diels-Alder oligomers linked by polysulfide chains. Polysulfides with four or more sulfur atoms have a variety of useful properties and have been employed as industrial lubricants, sealants in the glass-insulation industry, and binders in solid propellants for rockets (e.g., Thiokol A, (CH₂CH₂S₄)_n). In the vulcanization of rubber, polyolefins are converted to an elastomeric substance with desirable mechanical properties by cross-linking the chains with two or more sulfur atoms.

Thiocarbonyl compounds

The thiocarbonyl functional group (―C(=S)―), analogous to the carbonyl group, is found in thioaldehydes and thioketones, as well as in a variety of compounds with nitrogen or oxygen (or both) attached to the thiocarbonyl carbon (e.g., ―XC(=S)Y―, where X and Y = N or O). These compounds are named by analogy with the corresponding oxygen compounds—e.g., thioacetone, CH₃C(=S)CH₃, or 2-propanethione. Many thiocarbonyl compounds tend to be deeply coloured and highly reactive, owing to the fact that the double bond (π bond) between carbon and sulfur uses orbitals of quite different sizes (2p on carbon and 3p on sulfur), which do not overlap well. The parent thiocarbonyl compound, thioformaldehyde (CH₂=S), is extremely reactive and cannot be isolated. However, it is very stable in the gas phase in low concentrations and is formed when various small organosulfur compounds are heated to extremely high temperatures. Thioformaldehyde has been detected in interstellar space by radio astronomers. Carbon disulfide, S=C=S, is a common and important organic solvent and raw material containing a thiocarbonyl group; it is used in the manufacture of rayon. Isothiocyanates, R―N=C=S, have cumulated bonding similar to that in carbon disulfide. Allyl isothiocyanate, CH₂=CHCH₂N=C=S, gives horseradish its distinctive flavour; related compounds are found in mustard and radish. The dithiocarbamate thiuram, R₂NC(S)SSC(S)NR₂ (R = CH₃), is used as an antioxidant and accelerator in rubber vulcanization and is also employed as an insect repellent and fungicide. The related compound disulfiram (Antabuse; R = CH₂CH₃) is used in treating alcoholism. A thioamide, ethionamide, is an important drug used in the treatment of tuberculosis, and other thioamides are used as peptide analogs and in peptide synthesis.