The application of pressure to solutions of polyethylene oxide in water causes phase separation through spinodal decomposition similar to that observed when the temperature is raised above the lower critical solution temperature. This phase separation pressure is dependent on molecular weight but independent of concentration. Viscosity measurements indicate a continuous decrease in the radius of gyration from good to theta solvent conditions as pressure is increased. This pressure-induced loss of solvent quality is a result of the loss of the ability of water to form hydrogen bonds at high pressure and the resulting changes in hydrophobic interactions.PACS numbers: 61.25.Hq, 64.75.+g, 35.20.Gs, Understanding the configuration of macromolecules in water-based solutions is fundamental to many technologies as well as to much of biology. Because of the presence of electrostatic, dipole, and hydrophobic interactions as well as hydrogen bonding the conformation of aqueous polymers can show additional complexity typically not seen in nonaqueous polymers. An example of how these forces can influence configuration is given in living organisms where the cooperative eff*ect of these interactions produces quite specific polymer chain configurations, and the resulting secondary and tertiary structures (which are known to change under pressure) [1] are responsible for a biomacromolecule's activity. The solution properties of polyethylene oxide (PEO) allow the examination of two of these forces, hydrogen bonding and hydrophobic interactions, without complications from the myriad interactions arising from multifunctional biomolecules. Nevertheless, PEO in water shows complex solution behavior manifested in its unusual phase behavior, a closed-loop temperature-concentration phase diagram at low molecular weight and a lower critical solution temperature (~100°C) for longer chain length [2]. This has attracted recent theoretical interest [3,4]. In addition, the solution behavior of PEO itself leads to many technical applications [5] including its use as a drag reducer.Under ambient conditions PEO in water is in several ways a typical example of a polymer good solvent system. The random coil nature of PEO in water has recently been unambiguously demonstrated [6]. For example, the scaling exponents /?^ocM^^^^ /?/, ocM^^"^', and Ai (xM ~^-^^ are all found to be in excellent agreement with theoretical predictions for polymers in good solvents [7]. One unusual feature of PEO in water is that the second osmotic virial coefficient A 2 is unusually large, reflecting an anomalous swelling of the chains [7,8]. This is attributed to the strong water-PEO interaction through hydrogen bonding. An ambient-temperature hydration number of 2-3 water molecules per PEO monomer unit has been reported [9][10][11]. This unusually strong hydrogen bonding plays a pivotal role in the water solubility of PEO; for example, the structurally similar polypropylene oxide has relatively weaker hydrogen bonding and thus is insoluble in water [12]. The eff'ect of el...