Elemental sulfur, in the presence of a nickel(II) catalyst, can add across the strained alkene of norbornene and its derivatives, providing cyclic polysulfide products in which the vicinal C-S bonds have a cis stereochemical relationship (S2-S18). It was envisioned that these well-defined polysulfides would provide a good testing ground for electrochemically-induced ring-opening polymerization as an alternative to inverse vulcanization in accessing polysulfide polymers. Trisulfide 1, as a monomer with high symmetry, was anticipated to simplify spectroscopic analysis of the reaction and products. Monomer 1 and polymers derived from 1 are also high in sulfur content (50 wt% sulfur), which is comparable to many polymers made by inverse vulcanization. Monomers 3 and 4 were made to assess functional group tolerance and also provide a handle for post-polymerization modification. Trisulfides 1, 3 and 4 were therefore prepared by adapting the method previously reported by Poulain (Fig. ). Pentasulfide monomer 2 was isolated as a minor product in the preparation of trisulfide monomer 1. The cyclic sulfides were purified by vacuum distillation or flash column chromatography providing monomer 1 as an oil and monomers 2-4 as crystalline solids. All monomers were characterized by NMR, IR, and Raman spectroscopy, mass spectrometry, and elemental analysis (S6-S18).