The synthesis and characterization of poly(phenylene polysulfide) networks (PSNs) with controlled average sulfur ranks, from elemental sulfur (ES) and p-diiodobenzene (DIB), are investigated. The PSN films, prepared via simple hot pressing, are found to possess large extensibility up to around 300% and complete recovery of shape and mechanical properties after deformation, which are attributed to the loosely cross-linked network structures mainly consisting of linear poly(phenylene polysulfide) chains. The covalent polysulfide linkages in the PSNs also exhibit dynamic behaviors under ultraviolet (UV) or thermal treatment, thus, enabling self-healing and reprocessing of the films when scratched and broken, respectively. Combined with the unique mechanical properties of the PSNs, their high refractive index and excellent infrared (IR) transparency contribute to the preparation of stretchable, healable, and reprocessable IR transmitting materials for potential deformable and stretchable optical applications.