Photoresponsive polymers have attracted extensive attention due to their tunable functionalities and advanced applications; thus, it is significant to develop facile in situ synthesis strategies, extend polymers family, and establish various applications for photoresponsive polymers. Herein, we develop a catalyst-free spontaneous polymerization of dihaloalkynes and disulfonic acids without photosensitive monomers for the in situ synthesis of photoresponsive polysulfonates at room temperature in air with 100% atom economy in high yields. The resulting polysulfonates could undergo visible photodegradation with strong photoacid generation, leading to various applications including dual-emissive or 3D photopatterning, and practical broad-spectrum antibacterial activity. The halogen-rich polysulfonates also exhibit a high and photoswitched refractive index and could undergo efficient postfunctionalizations to further expand the variety and functionality of photoresponsive heteroatom-containing polyesters.