In this work, we investigated the oxygen permeation properties of barium bismuth iron oxide within the family of [Ba(2-3x)Bi(3x-1)][Fe(2x)Bi(1-2x)]O(2+3x/2) for x = 0.17-0.60. The structure changed progressively from cubic to tetragonal and then to hexagonal as function of x in accordance with the different relative amounts of bismuth on A-site and B-site of ABO(3-delta),5 perovskite lattices. We found that the oxygen flux and electrical conductivity correlated strongly, and it was prevalent for the cubic structure (x = 0.33-0.40) which conferred the highest oxygen flux of 0.59 ml min(-1) cm(-2) at 950 degrees C for a disk membrane x = 0.33 with a thickness of 1.2 mm. By reducing the thickness of the disk membrane to 0.8 mm, the oxygen flux increased to 0.77 ml min(-1) cm(-2), suggesting both surface kinetics and ion diffusion controlled oxygen flux, though the former was more prominent at higher temperatures. For disk membranes x= 0.45-0.60, the perovskite structure changed to tetragonal and hexagonal, and the oxygen flux was insignificant below 900 degrees C, clearly indicating electron conduction properties only. However, for two compositions with relatively high bismuth content, e.g. x=0.55 and 0.60, there was a sudden and significant rise of oxygen permeability above 900 degrees C, by more than one order of magnitude. These materials changed conduction behavior from metallic to semiconductor at around 900 degrees C. These results suggest the advent of mixed ionic electronic conducting properties caused by the structure transition as bismuth ions changed their valence states to compensate for the oxygen vacancies formed within the perovskite lattices. (C) 2010 Elsevier B.V. All rights reserved.