Phase inversion spinning technique was employed to prepare dense perovskite hollow fiber membranes made from composition BaCoxFeyZrzO3-delta (BCFZ, x+y+z=1.0). Scanning electron microscope (SEM) shows that such hollow fibers have an asymmetric structure, which is favored to the oxygen permeation. An oxygen permeation flux of 7.6 cm(3)/min cm(2) at 900 degrees C under an oxygen gradient of 0.209 x 10(5) Pa/0.065 x 10(5) Pa was achieved. From the Wagner Theory, the oxygen permeation through the hollow fiber membrane is controlled by both bulk diffusion and surface exchange. The elements composition of fresh fiber and the fiber after long-term experiments were analyzed by energy-dispersive X-ray spectra (EDXS). Compared to the fresh fiber, sulphur was found on the tested hollow fiber membrane surface exposed to the air side and in the bulk, and Ba segregations occur on the tested hollow fiber membrane surface exposed to the air side. A decrease of the oxygen permeation flux was observed, which was probably due to the sulphur poisoning. (c) 2006 Elsevier B.V. All rights reserved.