In summary, this work presented a compelling study of employing a flexible-robust MOF to achieve highly efficient C₃F₆/C₃F₈ separation through a temperature-modulated gating mechanism. Here, they emphasize the important role of temperature-dependent gate-opening adsorption behavior and elucidate the host-guest interactions through a combination of experimental, single-crystal structural, and theoretical computational analyses. This finding provides a valuable idea for harnessing the flexibility of porous adsorbents and distinct host-guest interactions to effectively separate important and challenging industrial gas mixtures.