Establishing new energy-saving systems for gas separation using porous materials is indispensable for ensuring a sustainable future. Herein, we show that ELM-11 (Cu(BF ) (4,4'-bipyridine) ), a member of flexible metal-organic frameworks (MOFs), exhibits rapid responsiveness to a gas feed and an 'intrinsic thermal management' capability originating from a structural deformation upon gas adsorption (gate-opening). These two characteristics are suitable for developing a pressure vacuum swing adsorption (PVSA) system with rapid operations. A combined experimental and theoretical study reveals that ELM-11 enables the high-throughput separation of CO from a CO /CH gas mixture through adiabatic operations, which are extreme conditions in rapid pressure vacuum swing adsorption. We also propose an operational solution to the 'slipping-off' problem, which is that the flexible MOFs cannot adsorb target molecules when the partial pressure of the target gas decreases below the gate-opening pressure. Furthermore, the superiority of our proposed system over conventional systems is demonstrated.