Recently, the reported Perovskite/Ruddlesden-Popper composite with significant improvement of oxygen surface kinetics has been adopted into gas separation process. Here, we report a novel La0.7Sr0.3FeO3 - delta/(La0.5Sr0.5)(2)CoO4 + delta (LSF-LSC) composite hollow fiber membrane (HFM), which was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and thermal expansion test, etc. The O-2 permeation test results indicated that, under sweeping gas of pure He (100 mL min(-1)), the composite HFM exhibited the superior O-2 permeability (0.72 mL min(-1) cm(-2)) at the temperature of 950 degrees C with respect to the single La0.7Sr0.3FeO3 - delta (LSF) membrane, acid-etched membrane, and (La0.5Sr0.5)(2)CoO4 + delta (LSC)-coated membrane. Moreover, the composite membrane exhibited high CO2 tolerance as well as phase stability. The generation of hetero-interface between Ruddlesden-Popper phase and perovskite phase could be responsible for the improvement of the oxygen transportation over the fabricated composite membrane.