Raman and infrared (IR) spectra of solutions of LiClO4 in ethylene carbonate (EC) have been measured. Spectral changes of the ring-bending mode of EC with different LiClO4 contents are analyzed and an average solvation number of six is suggested for the Li+ ions in EC. Band splittings occur for the nu(1), nu(2), and nu(4) modes of the perchlorate anion (at ca. 933, 462, and 624 cm(-1) for free ClO4- anion in the Raman spectrum, respectively). In the meantime the nu(1) and nu(4) modes are activated in the IR spectrum. These reveal a perturbation (change in symmetry) of the ClO4- anions and formation of contact ions in concentrated solutions.