Abstract The sorption and permeation of carbon dioxide gas in miscible blends of poly(phenylene oxide) and polystyrene was measured as a function of pressure at 35°C over the entire range of blend compositions. The results are well described quantitatively by the dual sorption and dual mobility models developed for glassy polymers. The Henry's law sorption parameter was analyzed by the Flory—Huggins theory of ternary mixtures to obtain an interaction parameter which quantifies the exothermic heat of mixing for this blend system. The Langmuir capacity term was successfully related to the unrelaxed volume of the glassy blends. Transport properties of the blends were found to lie well below predictions based on simple additivity which is consistent with the strong interaction between the two polymers.