The sequestration of trace hexafluoropropylene (C3F6) is a critical yet formidable task in the production of high-purity perfluoropropane (C3F8), an important perfluorinated electronic specialty gas (F-gas) in the advanced electronics industry. Traditional adsorbents struggle with uneven, low-pressure uptake and compromises in selectivity. This work utilizes aperture size-electrostatic potential matching within a robust metal-organic framework (Al-PMA) to facilitate selective, reversible binding of C3F6 while excluding larger C3F8 molecules. The presence of bridging hydroxyl groups (μ2-OH) in Al-PMA creates positive electrostatic potential traps that securely anchor C3F6 through strong hydrogen bonding, evidenced by in-situ infrared and 19F magic angle spinning nuclear magnetic resonance spectroscopy. Breakthrough experiments demonstrate the efficient removal of trace C3F6 from C3F8 under ambient conditions, achieving C3F8 purity exceeding 99.999%. The scalability of Al-PMA synthesis, remarkable stability, and exceptional performance highlight its potential as a promising adsorbent for industrial C3F6/C3F8 separations.