The RAFT polymerization of 2,2,2-trifluoroethyl α-fluoroacrylate (FATRIFE) was investigated under thermal conditions and light irradiation. The performances of 4 different chain transfer agents (3,5-dimethyl-1H-pyrazole-1-carbodithioate (CTA 1), 4-cyano-4-(2-phenylethanesulfanylthiocarbonyl)sulfanylpentanoic acid (CTA 2), dibenzyl trithiocarbonate (CTA 3), and Ethyl 2-(phenylcarbonothioylthio) propionate (CTA 4)) were compared under thermal conditions. CTA 2 afforded relatively good control of the polymerization with relatively low dispersities (apparent molar mass M n,SEC ~ 37.8 kg/mol vs. PMMA, Đ < 1.10). Pseudo-first-order polymerization kinetics and a linear increase of the molar masses versus monomer conversions were observed. The RAFT polymerization of FATRIFE was further explored under photoirradiation using CTA 2 as chain transfer agent and white LED lamps (14 W × 2) irradiation. In the absence of exogenous radical sources or catalysts, controlled polymerization was observed at room temperature. Linear increase of molar masses (up to 25.3 kg/mol) with monomer conversions and low dispersities (Đ < 1.10) were successfully obtained. Temporal control of the polymerization was also observed using light ON/OFF experiments. Poly(FATRIFE) based macroCTA synthesized by photoRAFT was also extended with 1,1,1,3,3,3-hexafluoropropan-2-yl 2-fluoroacrylate and tert-butyl-2-trifluoromethacrylate/FATRIFE.