The kinetics of the F₂ reaction with thiirane (C₂H₄S) was studied for the first time in a flow reactor combined with mass spectrometry at a total helium pressure of 2 Torr and in the temperature range of 220 to 800 K. The rate constant of the title reaction was determined under pseudo-first-order conditions, either monitoring the kinetics of F₂ or C₂H₄S consumption in excess of thiirane or of F₂, respectively: k₁ = (5.79 ± 0.17) × 10⁻¹² exp(−(16 ± 10)/T) cm³ molecule⁻¹ s⁻¹ (the uncertainties represent precision of the fit at the 2σ level, with the total 2σ relative uncertainty, including statistical and systematic errors on the rate constant being 15% at all temperatures). HF and CH₂CHSF were identified as primary products of the title reaction. The yield of HF was measured to be 100% (with an accuracy of 10%) across the entire temperature range of the study. Quantum computations revealed reaction enthalpies ranging from −409.9 to −509.1 kJ mol⁻¹ for all the isomers/conformers of the products, indicating a strong exothermicity. Boltzmann relative populations were then established for different temperatures.