Self-diffusion and sorption of seven gases (He, H-2, O-2, N-2, CH4, CO2, and Xe) in poly[bis(2,2,2-trifluoroethoxy)phosphazene] (PTFEP) have been investigated by molecular dynamics and Grand Canonical Monte Carlo (GCMC) simulations of two amorphous cells and an α-orthorhombic crystalline supercell. In the case of MD simulation of diffusion coefficients, values obtained for both amorphous and crystalline PTFEP are similar and comparable to experimental values reported for semicrystalline samples. These results indicate that gas diffusion is unrestricted in the crystalline state of PTFEP as has been reported for poly(4-methyl-1-pentene) (PMP) and, more recently, for a crystalline form of syndiotactic polystyrene (sPS). In contrast to both PMP and sPS that have low-density crystalline forms, only He exhibits any solubility in the a-orthorhombic crystalline cells of PTFEP during simulation. In addition, values of the solubility coefficients obtained from simulation of the amorphous cells are three to five times larger than would be expected by extrapolating values reported for semicrystalline samples to 100% amorphous content. These results suggest that while the crystalline domains do not restrict gas diffusivity in PTFEP, they significantly reduce gas solubility in semicrystalline PTFEP through the reduction of amorphous content and through some additional effect of the crystallites on amorphous-phase solubility, possibly through chain immobilization of the amorphous phase. Similar solubility behavior has been suggested for polyethylene on the basis of recent simulation studies. As reported in a prior communication, the solubility of CO2 in PTFEP is very high compared to other gases due to a weak quadrupole-dipole interaction between CO2 and the trifluoroethoxy group of PTFEP. As a result, the solubility coefficients of CO2 obtained from GCMC simulation of the amorphous cells and from permeability measurements of semicrystalline samples are both larger than predicted by a simple correlation of gas solubility coefficients with the Lennard-Jones potential well parameter, elk, of other gases as proposed by Teplyakov and others. A modified form of this correlation that includes a Flory interaction term is shown to fit all gas solubility data for this polymer including that of CO2. © 2005 Elsevier Ltd. All rights reserved.