Natural gas decarburization is an important issue as CO2 reduces its energy density and corrodes equipment with humidity. Here, we used PAF-1 as pours platform and derived PAF-1-SO3Co as an efficient and stable CO2/CH4 separation material by introducing cobalt sulfonate groups. Particularly, transition metal cobalt owns rich d-electron orbit and interacts with polar molecules evidently, which is suitable for improving the interaction between polar adsorbate and adsorbent. The experiment results further demonstrate this rule and show that the selectivity of PAF-1-SO3 Co reaches 14.27 at 298 K and 1 bar, which has increased almost 5 times than PAF-1. Importantly, PAF-1-SO3Co exhibits remarkably high regenerability (75%) and sorbent selection parameter (S, 85.8). Moreover, PAF-1-SO3Co has dramatically high working stability, whose adsorption performance shows ignorable decrease after soaking in simulated acidic environment even for 1 week Accordingly, PAF-1SO(3)Co is a promising adsorbent for separation and purification of CO2 from natural gas.