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Realization of ethane-selective porous materials for efficient ethane/ethylene (C2H6/C2H4) separation is an important task in the petrochemical industry. Although a number of C2H6-selective adsorbents have been realized, their adsorption capacity and selectivity might be mostly dampened under humid conditions due to structure decomposition or co-adsorption of water vapor. A desired material should have simultaneously high C2H6uptake and selectivity, excellent water stability, and ultralow water adsorption uptake for industrial applications, but such a material is elusive. Herein, we report a chemically stable hafnium-based material (Hf)DUT-52a, featuring the suitable pore apertures and less hydrophilicity for highly efficient C2H6/C2H4separation under humid conditions. Gas sorption results reveal that (Hf)DUT-52a exhibits both high ethane adsorption capacity (4.02 mmol g−1) and C2H6/C2H4selectivity (1.9) at 296 K and 1 bar, which are comparable to the majority of the top-performing materials. Most importantly, the less pore hydrophilicity enables (Hf)DUT-52a to exhibit a negligible water uptake of 0.036 g g−1before 40% relative humidity (RH), effectively minimizing the impact of humidity on separation capacity. This material thus shows excellent separation capacity even under 40% RH with a high polymer-grade ethylene production capacity up to 8.43 L kg−1at ambient conditions, as evidenced by the breakthrough experiments.