Sulfur-containing polymers have shown promise as redox and light responsive, sensorics as well as chemically recyclable materials with improved thermal and optical properties as compared to their non-sulfurated counterparts. In the societal context, it is beneficial to access these directly from S8, which is a megaton scale waste product of the petrochemical industry from oil refining (Figure (a)), or from high sulfur-wt% base chemicals sourced from S8 such as carbon disulfide CS2. Consequently, a great deal of effort is currently concerned with the synthesis of useful polymeric materials from S8 itself or chemicals directly sourced from S8. For example, many crosslinked polymers have been synthesized in recent years through inverse vulcanization which have found numerous applications as lenses, electrodes, elastomers, heavy metal scavengers and reprocessable thermosets. Although linear thermoplastics can be prepared via different (typically polycondensation) methods, these often require expensive or highly reactive reagents, only incorporate low amounts of sulfur or yield oligomers. Given the cyclic structure of S8, one might imagine that ring-opening polymerisation would be suitable to produce polysulfur Sn, however this process is thermodynamically unfavourable at ambient condition (floor temperature 159 °C) and requires copolymerisation techniques to obtain stable polymers. H NMR spectra (CDCl3, 400 MHz) of polymers corresponding to Table run #1 and #3. * Denotes residual DCM from purification. # residual H2O. (b) H- C HMBC NMR spectra of polymer corresponding to Table run #1.