The construction of high‐performance MOF‐based hollow fiber composite membrane (HFCM) modules is a significant, yet challenging task for the biofuel production industry. In this study, a novel approach was taken to fabricate PDMS@ZIF‐8/PVDF HFCMs in modules through a facile ZIF‐8 self‐crystallization synthesis followed by pressure‐assisted PDMS infusion for pervaporation ethanol‐water separation. The as‐prepared HFCMs exhibited an ultrathin separation layer (thickness, 370 ± 35 nm), which was achieved through precise regulation of the ZIF‐8 membrane and defect repair by PDMS infusion. Moreover, the strategy utilized in this study resolved the defect issues arising from MOF agglomeration in conventional composite membranes. Impressively, at the optimal packing density, the prepared membrane demonstrated a remarkable ethanol flux (1.11 kg m−2 h−1) with an PSI value (26.59 kg m−2 h−1) and showed promising long‐term stability for the pervaporation of 5 wt% ethanol aqueous solution at 40°C.