2,2'-Bis ( 3,4-dicarboxyphenyl ) hexafluoropropane dianhydride ( 6FDA )-1, 3-phenylenediamine ( mPDA ) polyimide was synthesized by chemical imidization in a two-step procedure. The density of the polymer dense membrane, the fractional free volume and the glass transition temperature were measured. The ultra-thin hollow fiber membranes with a dense skin were fabricated with different air gap. The hollow fiber membranes have an O(2) permeance of 19. 10 GPU and a CO(2) permeance of 106. 34 GPU with the O(2)/N(2) selectivity of 5. 99 and the CO(2)/CH(4) selectivity of 82. 00 at 25 degrees C, 0. 5 MPa. The calculated thickness of the dense skin based on O(2) permeance is 96 nm. The temperature effect on the gas separation performance was investigated. The permeances of the O(2), N(2), CH(4) and CO(2) increase with an increase in temperature, while the selectivities of O(2)/N(2) and CO(2)/CH(4) decrease. The physical aging phenomenon of the asymmetric hollow fiber membranes spun with different air gap distances was investigated. The results show the permeance of the ultra-thin membranes sharply decreases and the selectivity increases. And the thickness of the dense skin affected the aging behavior.