This allotrope was first prepared by M. R. Engel in 1891 by treating thiosulfate with HCl.

[4] Another method of preparation involves the reaction of a polysulfane with sulfur monochloride:[3] The name hexasulfur is the most commonly used and preferred IUPAC name and is constructed according to the compositional nomenclature, and cyclohexasulfane.

It is also the final member of the thiane heterocyclic series, where every carbon atom is substituted with a sulfur atom, thus the systematic name hexathiane, a valid IUPAC name, is constructed according to the substitutive nomenclature.

Another valid IUPAC systematic name cyclo-hexasulfur is constructed according to the additive nomenclature.

Hexasulfur adopts a chair configuration similar to that of cyclohexane, with bond angles of 102.2°.