This work presents the structural properties of gas permeation of a group of polyurethane membranes. All polymers were synthesized using a 1:3:2 molar ratio of polyol:diisocyanate: chain extender. The obtained results from Fourier transform infrared spectrometer (FT-IR) of polymers indicate that by changing the diisocyanate from aromatic to linear aliphatic, the microphase separation of hard and soft segments increases. Study of the differential scanning calorimetery (DSC) and X-ray diffraction (WAXD) patterns confirmed that PTMG and PCL polyols can be arranged in small crystalline structures. Furthermore, a hard ordered segment in crystal phase could be obtained, owing to the high phase separation of the polymer based on HDI. Permeation measurements of polymers revealed that the permeability of gases increases with microphase separation in polymer and selectivity of gases drops down. Polymers based on PPG showed the highest phase separation and permeability. The obtained results revealed more phase mixing of the polymer based on DMPA chain extender in comparison to BDO, which lead to lower permeability and higher selectivity. The solubility and diffusivity of gases indicate solubility domination of gas transport in these membranes. The observed solubility domination increases by phase separation. The results of permeability tests indicate high permeability, up to 186 Barrer (1 Barrer = 1 x 10(-10) [cm(3) (STP) cm/cm(2) s cmHg]), and high selectivity for carbon dioxide with respect to nitrogen (CO2/N-2:45). Our data sheds light on gas permeation properties of polyurethane membranes. (C) 2011 Elsevier B.V. All rights reserved.