Neutron diffraction with isotopic substitution was used to assess the relative solvation interactions near lithium ions in a D2O/deuterated poly(ethylene oxide) (PEO) mixed solvent near 25degreesC. Results for local structure near Li+ indicate a hydration structure very similar to that observed previously for Li+ in D2O solution with no added polymer. For the mixed solvent ratio used, PEO does not compete effectively with D2O for solvation sites near Li+. These results contribute to our understanding of reactivity and transport of ionic species in mixed aqueous polymer systems.