Recovery and separation of anthropogenic emissions of electronic specialty gases (F-gases, such as CF 4 and SF 6 ) from the semiconductor sector are of critical importance. In this work, the hierarchical porous UiO-66-Br 2 @PS/DVB-packed column was constructed by a high internal phase emulsions strategy. UiO-66-Br 2 @PS/ DVB exhibits a superior selectivity of CF 4 /N 2 (2.67) and SF 6 /N 2 (3.34) predicted by the IAST due to the diffusion limitation in the micropore and the gas-framework affinity. Especially, UiO-66-Br 2 @ PS/DVB showed significant CF 4 and SF 6 retention and enabled the successful separation of CF 4 /N 2 and SF 6 /N 2 with a resolution of 2.37 and 8.89, respectively, when used as a packed column in gas chromatography. Compared with the Porapak Q column, the HETP of the UiO-66-Br 2 @PS/DVB-packed column decreased and showed good reproducibility. This research not only offers a convenient method for fabricating a hierarchical porous MOF-packed column but also showcases the prospective utilization of MOFs for the separation of the F-gas/N 2 mixture.