Glassy polymers usually have low-to-moderate sorption levels that make it difficult to accurately analyze the minute amount of the permeant sorbed in the polymer. This article discusses an experimental procedure to obtain mixed-liquid sorption isotherms of methanol and methyl tert-butyl ether (MTBE) in glassy 6FDA-ODA polyimide via extraction and head-space analysis. The organics are extracted from the glassy polymer with 5 wt % N,N-dimethyl acetamide (DMAc) in water. The incorporation of DMAc, a known swelling agent for the polymer studied, expedites the desorption of organics from the glassy polymer. The concentration of the organics in the extract are then analyzed with gas chromatography head-space analysis. The suitability of this method is compared with the suitability of various other methods.