Calculated and experimental rotational spectra of 3,3,3-trifluoro- and 2,2,3,3-tetrafluoropropionyl chloride

► We record the first pure rotational spectra for 3,3,3-trifluoropropionyl chloride and 2,2,3,3-tetrafluoropropionyl chloride. ► We only observe the lowest energy conformers for each species under the conditions of the experiment. ► We have performed quantum chemical calculations to aid in the spectroscopy.