Supercritical fluids (SCFs) have great technological potential for minimizing the organic wastes associated with polymer manufacturing and processing. However, significant challenges remain for developing the same level of understanding of the behavior of polymers in SCFs as has been reached for polymers in traditional organic solvents. Small-angle neutron scattering was used to study the effect of pressure and temperature on the phase behavior of poly(dimethylsiloxane) (PDMS) in supercritical carbon dioxide (SC CO2). It was demonstrated that PDMS-SC CO2 solutions reproduce all main features of the temperature-concentration phase diagram for polymers in organic solvents. Moreover, because of their continuously adjustable solubility, SCFs exhibit novel effects, such as a pressure-induced transition to the Theta point and to the good solvent domain, in addition to a polymer-solvent demixing at a lower critical solution pressure.