Controlled Radical Copolymerization of Hydrofluoroolefin 2,3,3,3‐Tetrafluroropropene (R1234yf) via Thermally Activated Delayed Fluorescence Catalysis

= 31.02 µs) and high quantum yield after excitation. The TADF catalyst facilitated oxidative quenching with a xanthate chain-transfer agent, enabling visible-light controlled radical copolymerization of 2,3,3,3-tetrafluoropropene (R1234yf) at ppm levels of catalyst usage under ambient conditions. The copolymerization furnished good control across various unconjugated comonomers (vinyl esters, vinyl amides), yielding HFO-embedded chains with tunable molecular weights, controlled dispersities and good chain-end fidelity. Furthermore, this versatile synthetic approach promoted on-demand construction of complex block architectures through chain-extension polymerization. After hydrolysis, the obtained amphiphilic chains exhibited outstanding performance as superhydrophobic coatings on diverse substrates, and surfactants in emulsion polymerization, supporting practical potentials of HFO-based copolymers. This work establishes a versatile platform to access well-defined R1234yf copolymers, creating opportunities to address both HFO-transformation concern and growing demand for high-performance fluoropolymers.