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Abstract The development of an organic optical glass, termed, disulfide glass (DSG), is reported as a new polymer for commodity plastic optics and thin film photonic applications. This low‐cost thermoset polymer possesses excellent transparency across the visible and infrared spectrum comparable to the best optical plastic to date, poly(methyl methacrylate), while having superior refractive index (n≈ 1.6). DSG can be fabricated into defect‐free, thick optical glass by bulk addition polymerization of two commodity monomers (sulfur monochloride, 1,3,5‐triallyl isocyanurate) via a new polymerization, sulfenyl chloride inverse vulcanization. The robust mechanical properties and optical clarity of DSG enable fabrication of precision optics (lenses, prisms) via diamond turn machining to demonstrate the manufacturability of DSG for commodity plastic optics. Finally, the synthetic modularity of DSG is demonstrated to form solution processable forms for the fabrication of thin film polymer photonic devices, negative tone polymer photoresists, and micropatterned arrays.