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Atactic polystyrene, isotactic polystyrene, and intermediate polyblend films of the homopolymers were cast from solutions of 1,3,5-trimethylbenzene (mesitylene) or o-chlorotoluene. Residual solvent content, glass transition temperatures, and densities of the polyblends were determined. Consequent to these preliminary characterizations, n-hexane absorption kinetics and equilibria in unannealed blends were determined; maxima in the plots of weight change versus time were apparent for all compositions. The maximum is a consequence of the ‘unlocking’ of previously trapped residual casting solvent consequent to plasticizing invasion by the n-hexane in the unannealed film specimens. Neutron activation analysis for chlorine confirmed that the o-chlorotoluene content in the films was reduced dramatically consequent to n-hexane absorption. Residual solvent content was also reduced by thermally annealing the films at 110°C for 48 h under a vacuum and, therefore, no maximum in the sorption/time behaviour was observed in thermally annealed samples nor in films previously contacted with n-hexane vapour and subsequently vacuum stripped. Both the rate of sorption and the apparent sorption equilibrium are greatly reduced as the isotactic polystyrene content is increased. Predominantly Case II or relaxation controlled absorption kinetics were observed in the polyblends consequent to thermal annealing and/or ‘solvent’ annealing. Although the form of the sorption kinetics was quite similar for absorption of n-hexane in thermally annealed or ‘solvent-annealed’ films, the sorption rate and amount of penetrant sorbed at apparent equilibrium were both larger for the thermally annealed films. These results suggest that the history dependence, which so frequently affects polymeric glasses, appears to confound a simple interpretation of the sorption experiments reported here. Consistent with observations in related systems, Super Case II kinetics were observed for the more slowly sorbing films which, in this case, contained isotactic polystyrene. Moreover, film whitening related to micro-voiding accompanied n-hexane sorption in blends containing atactic polymer; however, the whitening in the isotactic polymer was less pronounced and densification, presumably related to solvent induced crystallization, occurred consequent to long term exposure of the isotactic polymer to n-hexane.