Intrinsic viscosities [] were determined for five polystyrene samples ranging in molecular weight M w from 9:0 Â 10 4 to 1:2 Â 10 6 in toluene-supercritical carbon dioxide mixtures with different weight fractions of CO 2 (denoted as w(CO 2 )) at 40 C in a pressure range P ¼ 7:0{10:0 MPa using a rolling-ball viscometer. For every sample [] was a gradually increasing function of P, indicating that the polystyrene coil expands with increasing P. At fixed P and w(CO 2 ), the molecular weight dependence of [] was expressed in the form ½ / M w a . The exponent a remarkably changed with w(CO 2 ) at constant P; for example, it decreased from 0.68 (a good solvent value) to 0.42 (a poor solvent value below the theta point where a ¼ 0:5) with an increase in w(CO 2 ) from 15 to 31% at P ¼ 7:0 MPa. The solvent goodness was quantified in terms of the binarycluster integral determined by analyzing the [] data according to the two-parameter theory.KEY WORDS: Intrinsic Viscosity / High Pressure / Supercritical Liquid / Carbon Dioxide / Excluded-Volume Effect / Binary-Cluster Integral / Supercritical carbon dioxide (critical temperature 31.1 C and pressure 7.38 MPa) is known to be compatible with many organic solvents. Such mixtures, in which polymer solubility is controllable by changing the pressure and the solvent composition, 1-3 have possible applications to separation or blending of chemically different polymers and molecular weight fractionation of homopolymers. 4,5 For the purpose of industrial processing, the dependence of viscosity on temperature, pressure, and solvent composition was investigated for polymer + organic solvent + supercritical CO 2 systems.6,7 Most of these studies are, however, limited to rather high polymer concentrations (above 1 wt %) and fixed molecular weights M, and none of them discusses the effect of polymer chain dimensions or related molecular properties on ; of polymer solutions increases with increasing chain dimensions.The intrinsic viscosity [] of a polymer coil (i.e., a long flexible chain) is a basic molecular property related closely to the chain dimensions. It increases with an increase in M or solvent power (i.e., the strength of intramolecular excluded volume in a term of polymer statistical mechanics), but such dependence of [] in an organic solvent containing supercritical CO 2 has not been explored despite the importance to our understanding of the effect of supercritical CO 2 on polymer solution properties.In the present work, we determine [] for polystyrene (PS) samples in toluene-supercritical CO 2 mixtures as functions of molecular weight, solvent composition, and pressure higher than the boundary between one liquid phase and liquid-gas two phase regions. 4 The relation between the extent of chain expansion and the solvent condition is discussed on the basis of excluded-volume theories.8