Acquiring high C2H2 adsorption capacity and effectively separating it from the most difficult-to-separate byproduct CO2 in a dilute state are crucial for obtaining high productivity/purity monomer for polymers. Here, we address this challenge through topology regulation of fluorinated ultramicroporous metal–organic framework, producing a new hydrolytically stable adsorbent, ZUL-500. Uncovered by X-ray diffraction and modeling, a more favorable spatial distribution of GeF62- anions for C2H2 recognition is realized in sql topological ZUL-500 compare to ZU-32 with the same anion and metal node but pcu topology, offering remarkably increased C2H2 affinity and amplified C2H2/CO2 affinity difference that affords a dynamic exclusion of CO2 but excellent C2H2 adsorption in fixed-bed separation even for industrial-related mixtures (up to 8 components). Excellent values were simultaneously obtained for C2H2 uptake capacity, C2H2/CO2 separation factor and C2H2 productivity, coupled with good mass transfer and recyclability, providing exceptional productivity (2.92 ∼ 3.48 mmol g−1) of high purity (≥99.6%) C2H2 from mixtures.