Difunctional hollow fiber composite membranes (DHFCMs) with catalytic and separative properties were used as structured packing in reactive distillation to separate ethanol-water and to catalyze ethanol-acetic acid esterification without other catalysts. These fibers showed more excellent properties over conventional packing in the ethanol-water distillation, which worked 10-fold higher above the flooding limit that usually occurred in conventional cases. Also they showed similar properties with a membrane contactor using hollow fibers as structured packing. A small height of transfer unit (HTU) of 3.6 cm and the overall transfer coefficient K-G of 0.48 cm/s at the vapor velocity of 39.4 cm/s were obtained experimentally, which demonstrated a higher efficiency separating performance. The conversion of acetic acid reached 92% when DHFCMs with catalytic and separative properties were used as structured packing and without other catalysts in ethanol-acetic acid reactive distillation.