LAUSR

The growing demand for energy‐efficient natural gas purification necessitates advanced porous adsorbents that enable molecular precision in separating higher hydrocarbons C2H6/C3H8 from CH₄ while maintaining methane purity. Through rational π‐electron engineering of the framework structure, a microporous Co‐MOF is reported, constructed from pyridine carboxylic acid‐based aromatic ligands that achieve a benchmark C₂H₆/CH₄ selectivity of 83.8, ranking among the highest reported for MOF materials. The framework also demonstrates an exceptional IAST selectivity of 715.6 for C2H6/C3H8 (5/5) mixtures, coupled with high uptake capacities of 65.5 cm3·g⁻¹ for C₂H₆ and 65.8 cm3·g⁻¹ for C₃H₈ at 298 K and 100 kPa. This remarkable separation performance stems from the strategic incorporation of π‐electron aromatic ligands, which enhance the C‐H···π interactions with hydrocarbon molecules. Breakthrough experiments demonstrate practical viability, achieving 99.97% methane purity in the effluent stream. Molecular simulations confirm that the selective adsorption originates from optimized C‐H···π interactions and van der Waals forces between the framework and guest molecules, validating the rational design approach for high‐performance MOFs in industrial gas separation.