In this regard, Penczek and Duda (Figure )) reported in the late 1970s that S8 undergoes ringopening copolymerisation (ROCOP) with thiiranes under CdCO3 or NaSPh@18-crown-6 catalysis to form polysulfide of the type [-CR2-CH2-Sx-]n (R= H, Me; x = 1-9). Ren et al. very recently expanded this approach to PPNSbF6/MTBD catalysis to selectively yield polydisulfides. In both cases the key to S8 activation was that thiirane ring opening leads to a thiolate intermediate, which can open the S8 ring under formation of an anionic oligosulfide and then propagates. Again, these methodologies depend on the use of expensive or even noncommercial thiiranes. It would be much more attractive to be able to copolymerise S8 with the lighter homologous of thiiranes, namely epoxides, as some of these, e.g. propylene oxide PO, are large scale industrial chemicals. Unfortunately, epoxides do not copolymerise with S8 as the metalalkoxide intermediates formed from epoxide ring opening does not form stable intermediate or links with S8 (Figure )). However if one could generate thiolate intermediates in epoxide polymerisations their copolymerisation with S8 could be achieved. In this regard, Komber and Werner et al. reported that the lithium alkoxide-catalysed ROCOP of CS2/PO yields poly(monothio-alttrithiocarbonate)s (i.e. -O-C(=S)-O-or "OSO" groups in alternation with -S-C(=S)-S-or "SSS" groups, Figure )) rather than poly(dithiocarbonate)s with -O-C(C=S)-S-or "OSS" links. The polymers show an unusual head-to-head-alt-tail-to-tail sequence in that the tertiary "head" CH groups from PO ring opening sits next to OSO links and secondary "tail" CH2 groups sits next to SSS links. The sequence can be rationalised by an O/S exchange process at the chain end transforming lithium alkoxides into lithium thiolate intermediates and it is commonplace, albeit rarely controlled in the ROCOP of epoxides and oxetanes with sulfurated comonomers. Accordingly, we hypothesized that these thiolates might be capable of activating S8 to allow polymer formation from epoxides, S8 and CS2 which we report in this contribution.