The composition and structure of complexes that are formed in the system consisting of chlorinated cobalt dicarbollide (CCD), polyethylene glycol (PEG), and Sr²⁺ or Ba²⁺ in a polar diluent, dichloroethane or phenyl trifluoromethyl sulfone, were studied by IR and NMR spectroscopy. In extraction of Sr²⁺ and Ba²⁺ with solutions of [H ₅O ₂ ⁺·PEG]CCD^-, the organic phase contains the ionic associates [M²⁺·PEG]CCD ₂ ^- . The Sr²⁺ and Ba²⁺ complexes have similar composition and structure: The oxygen atoms of two OH groups and six COC groups of a PEG molecule fill the first coordination sphere of the metal ions. Also, no more than two water molecules can be coordinated in the second sphere, forming hydrogen bonds with the hydrogen atoms of two OH groups of PEG. The coordination of the OH groups of PEG with the Sr²⁺ and Ba²⁺ ions is preferable over the coordination of the COC groups, as follows from the fact that the extraction of Sr²⁺ and Ba²⁺ with CCD-PEG mixtures gets worse on replacement of the OH groups of PEG by other substituents. A considerable increase in the efficiency of Sr²⁺ and Ba²⁺ extraction with H-CCD solutions in the presence of PEG is due to the fact that all the H₂O molecules in the first coordination spheres of the M ²⁺ ions are replaced by the COC and OH groups of PEG with the formation of a hydrophobic complex [M²⁺·PEG](H ₂O)₂.