The facile and efficient functionalization of thermoresponsive polymers based on sequential, reversible thiol-exchange reactions is reported. Well-defined dithiomaleimide-containing polymers have been synthesized via Cu(0)-mediated SET-LRP and characterized by 1H NMR and size exclusion chromatography (SEC). The resulting thermosensitive copolymers were subsequently reacted with various thiols to demonstrate the applicability of the strategy, and the thiol-exchange reaction was found to be very fast and efficient. The cloud point of the prepared copolymers can be continually and reversibly tuned, and desirable functionality can be dynamically exchanged upon sequential addition of functional thiol reagents. Through the substitution by thioglucose, an ON-to-OFF switch for fluorescence of the copolymers along with the generation of a glycopolymer was achieved.