Ethylene (C₂H₄) purification from multi-component mixtures by physical adsorption is a great challenge in the chemical industry. Herein, we report a GeF₆^2-anion embedded MOF (ZNU-6) with customized pore structure and pore chemistry for benchmark one-step C₂H₄recovery from C₂H₂and CO₂. ZNU-6 exhibits significantly high C₂H₂(1.53 mmol/g) and CO₂(1.46 mmol/g) capacity at 0.01 bar. Record high C₂H₄productivity is achieved from C₂H₂/CO₂/C₂H₄mixtures in a single adsorption process under various conditions. The separation performance is retained over multiple cycles and under humid conditions. The potential gas binding sites are investigated by density functional theory (DFT) calculations, which suggest that C₂H₂and CO₂are preferably adsorbed in the interlaced narrow channel with high aff0inity. In-situ single crystal structures with the dose of C₂H₂, CO₂or C₂H₄further reveal the realistic host-guest interactions. Notably, rare C₂H₂clusters are formed in the narrow channel while two distinct CO₂adsorption locations are observed in the narrow channel and the large cavity with a ratio of 1:2, which accurately account for the distinct adsorption heat curves.