Stoichiometric ratios of poly(ethylene glycol) (PEG, M-w = 400) with poly(vinylpyrrolidone) (PVP, M-w =+/- 3.1 x 10(4) and M-w =1.25 x 10(6) M-w) were prepared from ethanol cast solutions and in supercritical CO2. The complex formation was studied via glass transition (T-g) analysis obtained from differential scanning calorimetry (DSC) thermograms. PEG-PVP blends were also loaded with ibuprofen. The molecular dispersion of ibuprofen, mechanism of interaction, the effect of CO2 pressure and temperature and ageing of blends were also analysed with DSC, attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray diffraction (XRD). T-g analysis indicated that supercritical CO2 can facilitate the formation of stoichiometric PEG-PVP complexes. Processing of PEG-PVP blends with ibuprofen results in the molecular dispersion of ibuprofen mainly bonded to PVP carbonyl groups, without significant disruption of the PEG-PVP complex. Increasing process pressure results in extraction of some PEG fractions. Post-processing ATR-FTIR shifts in ibuprofen-PEG-PVP complexes is greater with supercritical CO2 processing. These shifts are mainly attributed to atmospheric moisture absorption. Overall it was shown that, ibuprofen-loaded PEG-PVP complexes can be prepared from supercritical CO2 processing showing similar characteristics to such complexes prepared from solution casting. (C) 2011 Elsevier B.V. All rights reserved.