The flue gas from fossil fuel power plants is a long-term stable and concentrated emission source of CO 2 , and it is imperative to reduce its emission. Adsorbents have played a pivotal role in reducing CO 2 emissions in recent years, but the presence of water vapor in flue gas poses a challenge to the stability of adsorbents. In this study, ZIF-94, one of the ZIF adsorbents, showed good CO 2 uptake (53.30 cm 3 /g), and the calculated CO 2 /N 2 (15:85, v / v ) selectivity was 54.12 at 298 K. Because of its excellent structural and performance stability under humid conditions, the CO 2 /N 2 mixture was still well-separated on ZIF-94 with a separation time of 30.4 min when the relative humidity was as high as 99.2%, which was similar to the separation time of the dry gas experiments (33.2 min). These results pointed to the enormous potential applications of ZIF-94 for CO 2 /N 2 separation under high humidity conditions in industrial settings.