Triflate salts of Mg(II), Zn(II), and Cu(II) in Liquid, low weight poly(ethylene glycol) dimethyl ether (PEGM-(400)) to determine their conductivity and to ascertain their possible use as electrolyte media, have been studied. Their liquid structures have been studied by energy-dispersive X-ray diffraction. By this technique, the cation geometrical coordination has been determined. Furthermore, the local structure of the bivalent cations has been singled out by application of the difference method to isomorphic solutions. We found that the investigated cations have an octahedral coordination, with the exception of Cu, which displays two apical bonds longer than the planar ones. We also found that the polymer chain is coordinated to the cations Mg and Zn through the oxygen atoms of the polymer units 1, 5, and 9.