Zeolitic imidazolate frameworks (ZIFs) hold great promise in carbon capture, owing to their structural designability and functional porosity. However, intrinsic linker dynamics limit their pressure-swing adsorption application to biogas upgrading and methane purification. Recently, a functionality-locking strategy has shown feasibility in suppressing such dynamics. Still, a trade-off between structural rigidity and uptake capacity remains a key challenge for optimizing their high-pressure CO2/CH4 separation performance. Here, we report a sequential structural locking (SSL) strategy for enhancing the CO2 capture capacity and CH4 purification productivity in dynamic ZIFs (dynaZIFs). Specifically, we isolated multiple functionality-locked phases, ZIF-78-lt, -ht1, and -ht2, by activation at 50, 160, and 210 °C, respectively. We observed multiple-level locking through gas adsorption and powder X-ray diffraction. We uncovered an SSL mechanism dominated by linker-linker π-π interactions that transit to C-H···O hydrogen bonds with binding energies increasing from -0.64 to -2.77 and -5.72 kcal mol-1, respectively, as evidenced by single-crystal X-ray diffraction and density functional theory calculations. Among them, ZIF-78-ht1 exhibits the highest CO2 capture capacity (up to 18.6 mmol g-1) and CH4 purification productivity (up to 7.6 mmol g-1) at 298 K and 30 bar. These findings provide molecular and energetic insights into leveraging framework flexibility through the SSL mechanism to optimize porous materials' separation performance.