Cd(II) plus iodide species were extracted into PEG-rich phases in the aqueous PEG(1550)-(NH4)2SO4 system at pH 2.05–7.12. IR spectra show that increasing (NH4)2SO4 solution acidity does not protonate PEG ether oxygen atoms, but decreases water content in the PEG-rich phases. Metallic species’ extraction into the PEG predominantly alters how water molecules bind to polymer chains; the changes in their absorption bands depend on pH. Microscopy shows that “fixation” of the extracted metal in the PEG-rich phase occurs by specific interactions which depend on the species. These also determine changes in the polymer chains’ conformation.