Ionic conducting polymer gels prepared from PEG-grafted acrylates, ethylene carbonate (EC), dimethyl carbonate (DMC), and LiPF6 are studied by means of infrared and Raman spectroscopy. It is found that the presence of grafted PEO chains substantially changes the coordination of lithium cations from 'cation-solvent' to 'cation-polymer'. Spectroscopic studies show that Li+-PEO coordination is strongly favored in competition with the solvent molecules and dominates completely at ether oxygen to Li-cation ratios (O:Li) of 10:1 and 5:1. At an O:M of 4:1 a solvent-cation interaction arises, in agreement with previously reported MD calculations of a preferred coordination number of 5 in similar systems. The results suggest that the complex interactions which determine long time stability and ionic transport properties can be designed by functionalization of the polymer backbone in PMMA-based gel electrolytes. O 2000 Elsevier Science B.V. All rights reserved.