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The photo-oxidation of 2,2,2-trifluoroethyl acrylate (TFEA) (CH2CHC(O)OCH2CF3) initiated by OH radicals and Cl atoms was investigated in tropospheric conditions using both experimental and computational methods. The kinetic measurements were carried out in the temperature range of 268–363 K using the relative rate method. The rate coefficients for the reaction of OH radicals with TFEA were measured relative to diethyl ether, ethylene, and acetaldehyde. The rate coefficients for the reaction of Cl atoms with TFEA were measured relative to propylene and ethylene. The rate coefficients for the reaction of TFEA with OH radicals and Cl atoms at 298 K were experimentally measured to be kR1exp – 298 K = (1.41 ± 0.31) × 10–11 cm3 molecule–1 s–1 and kR2exp – 298 K = (2.37 ± 0.50) × 10–10 cm3 molecule–1 s–1, respectively. The deduced temperature-dependent Arrhenius expressions for the reactions of OH radicals and Cl atoms with TFEA are kR1exp – (268 – 363 K) = (9.82 ± 1.37) × 10–12 exp. [(812 ± 152)/T] cm3 molecule–1 s–1 and kR2exp – (268 – 363 K) = (1.25 ± 0.17) × 10–11 exp. [(862 ± 85)/T] cm3 molecule–1 s–1, respectively. To complement our experimental results, computational calculations were performed at CCSD(T)/cc-pVDZ//M062X/6-31+G(d,p) and CCSD(T)/cc-pVDZ//MP2/6-311+G(d,p) levels of theory, respectively, in combination with canonical variational transition-state theory (CVT) with small curvature tunneling (SCT) over the temperature range of 200–400 K. Furthermore, the degradation mechanisms initiated by OH radicals and Cl atoms were proposed for the titled reactions based on the qualitative analysis of the products in gas chromatography–mass spectrometry (GC–MS) and gas chromatography–infrared spectroscopy (GC–IR). Atmospheric implications, thermochemistry, and branching ratios for the titled reactions are discussed in detail in the paper.