Oxygen-enriched air has attracted increasing attention owing to its potential industrial application. In this work, ceramic hollow fiber-supported polydimethylsiloxane (PDMS) composite membranes were applied in separation of oxygen from air. The influence of PDMS layer thickness, pressure difference, temperature, and feed concentration on the oxygen-enriching performance was systematically investigated. The results indicated that the membrane (with the optimal PDMS layer thickness of 25 µm) achieved oxygen permeance of 104 GPU (1 GPU = 10 À6 cm 3 standard temperature and pressure (STP)/cm 2 s cmHg) with O 2 /N 2 ideal selectivity of 2.0 at room temperature and 0.1 MPa difference pressure. Over 10 days continuous operation, this enrichment performance kept stable, in which the oxygen concentration enriched from air can maintain about 30% by single-stage separation through the membrane. Our work demonstrated that the ceramic hollow fiber-supported PDMS composite membrane could be a competitive oxygen enrichment membrane for industry application.