A novel trithiocarbonate reversible addition−fragmentation chain transfer (RAFT) reagent, 3‐azidopropyl (4‐[fluorosulfonyl]benzyl)trithiocarbonate (Az‐FSBCT), which has both clickable azidopropyl and sulfonyl fluoride moieties, was designed and synthesized. Using the RAFT agent Az‐FSBCT and triethylboron as an initiator, well‐defined poly(N‐vinylpyrrolidone) (PVP), in which the azide and sulfonyl fluoride groups are at the α and ω positions of the polymer chains, were prepared without prior deoxygenation at room temperature. Moreover, the possibilities for the construction of new functionalized polymers were also demonstrated by a “click” copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) and sulfur(VI)‐fluoride exchange (SuFEx) postreaction using these terminal functional PVPs.