Fibers that can guide light are valuable tools for numerous applications, including telecommunications, remoting of optical components, and sensing. Specifically, optical waveguides are necessary components in integrated optical circuits, as well as in optical communications. Although polymer-based optical waveguides are common, they typically do not function in the infrared (IR) region of the electromagnetic spectrum. Rather, infrared waveguiding is typically accessed by utilizing chalcogenide glass materials (e.g., arsenic sulfide) or heavy-metal halide glass materials (e.g., indium fluoride). This report details the fabrication and use of sulfur-rich inorganic−organic hybrid polymers as optical waveguides and a demonstration of their use in the shortwavelength infrared (SWIR) region.