The interaction of lithium perchlorate with high molecular weight poly(ethylene oxide) (PEO) in dilute methanol solutions was studied using cloud point measurements, static and dynamic light scattering, and viscometry. For both good and poor solvent conditions, PEO/LiClO4 complexes form in coil outer portions and charge-charge repulsions between een these complexes swell the PEO coils and result in repulsive interactions between coils. A noteworthy consequence of this nonionic polymer --> polyelectrolyte conversion is the "salting in" of PEO in methanol by LiClO4.