Oxygen-selective perovskite hollow fiber membrane can be used to obtain an effective oxygen separation from air at high temperature (above 700 degrees C) for large scale application. Here, we display that oxygen permeation fluxes of La0.6Sr0.4CoO3 (LSC113) hollow fiber membrane was enhanced by macrostructure modification and (La,Sr)(2)CoO4 (LSC214) surface decoration. By changing the cross-section macrostructure from sandwich structure (for LSC-a fiber) to asymmetric structure (for LSC-b fiber), the oxygen flux was improved by up to 3.6-fold. Applying porous LSC214 decoration on LSC113 furthermore enhanced the oxygen fluxes for LSC-a and LSC-b, by up to 6.8-fold and 1.9-fold, respectively. (C) 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.