This work reports a detailed study of CO2 and N-2 adsorption and diffusion pathways on MFI-alumina hollow fibres and their role on both pure and mixture CO2/N-2 permeation. The hollow fibres have been prepared by pore-plugging hydrothermal synthesis starting from a clear solution with molar composition 1 SiO2: 0.45 TPAOH: 27 center dot 8H(2)O: xB(OH)(3) (x=0-0.02), showing a final nanocomposite architecture. A comprehensive screening has been performed to select the most suitable model for describing CO2 and N-2 adsorption and pure permeation in the (B)-MFI-alumina hollow fibres. The classical Ideal Adsorption Solution Theory (LAST) has been implemented to different permeation models to account for binary CO2/N-2 permeation within the fibres. (C) 2011 Elsevier Ltd. All rights reserved.