AbstractHydro‐chloro‐fluoro‐carbons (HCFCs) are potent greenhouse gases which strongly absorb the infrared (IR) radiation within the 8–12 μm atmospheric windows. Despite international policies schedule their phasing out by 2020 for developed countries and 2030 globally, HCFC‐132b (CH2ClCClF2) has been recently detected with significant atmospheric concentration. In this scenario, detailed climate metrics are of paramount importance for understanding the capacity of anthropogenic pollutants to contribute to global warming. In this work, the radiative efficiency (RE) of HCFC‐132b is experimentally measured for the first time and used to determine its global warming potential (GWP) over 20‐, 100‐ and 500‐year time horizon. Vibrational‐ and rotational‐spectroscopic properties of this molecule are first characterized by exploiting a synergism between Fourier‐transform IR (FTIR) spectroscopy experiments and quantum chemical calculations. Equilibrium geometry, rotational parameters and vibrational properties predicted theoretically beyond the double‐harmonic approximation are employed to assist the vibrational assignment of the experimental trace. Finally, FTIR spectra measured over a range of pressures are used to determine the HCFC‐132b absorption cross section spectrum from 150 to 3000 cm−1, from which istantaneous and effective REs are derived and, in turn, used for GWP evaluation.