The accelerator effect of amine activators N-methylimidazole and 4-vinylaniline (4-VA) on inverse vulcanization and dynamic covalent polymerization (DCP) has been investigated. The sulfur polymer with self-activation comonomer 4-VA could also be used for low temperature DCP to incorporate some volatile monomers. Those approaches provide a new synthetic and rate accelerated processes to activate S-8 for copolymerization processes with functional comonomers at lower temperatures and under a broader range of reaction conditions.