The chemical consists of rings of 8 sulfur atoms. It adopts a crown conformation with D point group symmetry. The S–S bond lengths are equal, at about 2.05 Å. Octasulfur crystallizes in three distinct polymorphs: rhombohedral, and two monoclinic forms, of which only two are stable at standard conditions. The rhombohedral crystal form is the accepted standard state. The remaining polymorph is only stable between 96 and 115 °C at 100 kPa. Octasulfur forms several allotropes: α-sulfur, β-sulfur, γ-sulfur, and λ-sulfur.
λ-Sulfur is the liquid form of octasulfur, from which γ-sulfur can be crystallised by quenching. If λ-sulfur is crystallised slowly, it will revert to β-sulfur. Since it must have been heated over 115 °C, neither crystallised β-sulfur or γ-sulfur will be pure. The only known method of obtaining pure γ-sulfur is by crystallising from solution.
Octasulfur easily forms large crystals, which are typically yellow and are somewhat translucent.