In this study, novel polymers of intrinsic microporosity (PIMs)-based hollow fiber structured packings were prepared by a facile pour-coating method and successfully applied as structured packings for isopropanol (IPA)/water distillation. The design of an ultrathin PIM-1 layer on the inner surface of hollow fibers effectively protected the membrane from mechanical damage, especially when assembled into the module. Based on the material properties and specific polymer chain structures, the hydrophobic PIM-1 layer made composite membranes to not only have a strong affinity for alcohols and moisture resistance but also possess a large surface area and excellent stability, which effectively decreased the membrane resistance and promoted the fast membrane transfer rate during the distillation process. The prepared PIM-1/PAN hollow fiber structured packings with a controllable defect-free PIM-1 layer down to 34 nm can be easily operated far beyond the normal flooding limit and achieve a very low height of a mass transfer unit (HTU) of 4.0 cm.