An excess of elemental sulfur is generated annually from hydrodesulfurization in petroleum refining processes; however, it
has a limited number of uses, of which one example is the production of sulfuric acid. Despite this excess, the
development of synthetic and processing methods to convert elemental sulfur into useful chemical substances has not
been investigated widely. Here we report a facile method (termed ‘inverse vulcanization’) to prepare chemically stable and
processable polymeric materials through the direct copolymerization of elemental sulfur with vinylic monomers. This
methodology enabled the modification of sulfur into processable copolymer forms with tunable thermomechanical
properties, which leads to well-defined sulfur-rich micropatterned films created by imprint lithography. We also
demonstrate that these copolymers exhibit comparable electrochemical properties to elemental sulfur and could serve as
the active material in Li–S batteries, exhibiting high specific capacity (823 mA h g21 at 100 cycles) and enhanced
capacity retention.