Defect engineering of metal–organic frameworks (MOFs) is a promising strategy for tailoring the interfacial characteristics between MOFs and polymers, aiming to create high‐performance mixed matrix membranes (MMMs). This study introduces a new approach using dual defective alkylamine (AA)‐modulated zeolitic imidazolate framework‐8 (DAZIF‐8), to develop high‐flux MMMs. Tributylamine (TBA) and triethylamine (TEA) monodentate ligands coordinate with zinc ions in varying compositions. A mixture of Zn(CH₃COO)₂·2H₂O:2‐methylimidazole (Mim):AA in a 1:1.75:5 molar ratio facilitates high‐yield coordination between Zn and multiple organic ligands, including Zn‐Mim, Zn‐TEA, and Zn‐TBA (>80%). Remarkably, DAZIF‐8 containing 3 mol% TBA and 2 mol% TEA exhibits exceptional characteristics, such as a Brunauer–Emmett–Teller surface area of 1745 m² g⁻¹ and enhanced framework rigidity. Furthermore, dual Zn‐AA coordination sites on the framework's outer surface enhance compatibility with the polyimide (PI) matrix through electron donor–acceptor interactions, enabling the fabrication of high‐loading MMMs with excellent mechanical durability. Importantly, the PI/DAZIF‐8 (60/40 w/w) MMM demonstrates an unprecedented 759% enhancement in ethylene (C₂H₄) permeability (281 Barrer) with a moderate ethylene/ethane (C₂H₄/C₂H₆) selectivity of 2.95 compared to the PI, surpassing the polymeric upper limit for C₂H₄/C₂H₆ separation.