Unexpected ultra‐efficiency for hexene/hexane separation derived from synergistic of “shielding” extractant

The efficient separation of α‐olefins from alkanes presents a significant challenge in the chemical industry. Conventional Ag + ‐based π‐complexation extraction suffers from poor selectivity due to high alkane solubility in organic solvents. This work proposes a novel “shielding extractant” concept by immobilizing Ag + in ethylene glycol (EG). The robust hydrogen bonding network of EG effectively excludes nonpolar alkanes, while Ag + exists as [Ag(EG)] + , retaining strong π‐complexation with olefinic C=C bonds. This coupled shielding‐complexation mechanism achieves a hexene/hexane performance index of 81, surpassing traditional solvents by 1–2 orders of magnitude. The extractant enables single‐stage enrichment of total olefins from simulated Fischer‐Tropsch oils to over 98 wt.% with excellent recyclability. A coupled extraction‐distillation process can deliver exceeding 98% olefin and 99.9% alkane products with 84.7% energy consumption reduced. This work provides a new, ultra‐efficient pathway for long‐chain olefin/alkane separation.