Polysulfate materials are efficiently constructed via SuFEx click chemistry, a versatile sulfur–fluorine exchange reaction enabling modular polymer assembly. Relying on programmable building blocks, this method facilitates rapid library construction and affinity-driven screening. The robust SuFEx-derived sulfate linkages confer excellent chemical stability, supporting the tailored fabrication of fibrous polysulfate materials with tunable intermolecular interactions and functional properties for advanced material applications.