Perfluoro-n-propane, perfluorocyclobutane, perfluoro-n-butane, and perfluoro-n-pentane are non-ozone-depleting industrial alternatives to chlorofluorocarbons and hydrochlorofluorocarbons. However, these perfluoroalkanes have significant band strength in the atmospheric window from 800 to 1200 cm−1. Coupled with their millennial-scale atmospheric lifetimes, they can lead to significant long-term global warming. Infrared spectra are required to quantify the climate impacts. This work provides a set of high-temperature infrared absorption cross-sections in the range 298–350 K at 0.1 cm−1 resolution from 515 to 1500 cm−1 for each compound. Our cross-sections generally agree with literature measurements except for perfluoro-n-pentane. We use density functional theory to calculate the absorption cross-sections from 0 to 515 cm−1 using the B3LYP functional and several basis sets. The 6-31G(d,p) basis set provides the best results for linear perfluoroalkanes, while the def2-TZVP basis set provides the best results for cyclic perfluoroalkanes. Using experimental cross-sections, we calculate the radiative efficiency and global warming potential for each compound, utilizing the Pinnock curve from Shine and Myhre (2020) and atmospheric lifetimes from Hodnebrog et al. (2020). These quantities are found to be independent of temperature. The average 100-year global warming potential derived from all cross-sections is 9,610±1,260, 10,800±1,420, 10,100±1,330, and 9,380±1,230 for perfluoro-n-propane, perfluorocyclobutane, perfluoro-n-butane, and perfluoro-n-pentane, respectively. Combining the data in this work with our previous measurements reveals that the global warming potential for perfluoroalkanes with an increasing number of CF bonds depends on the ratio of radiative efficiency to molecular weight.