Precise measurements on electrical conductances as well as laser Raman spectra in the wavenumber range 3500-100 cm(-1) of five lithium salts in 1,2-dimethoxyethane (DME) have been reported. The conductance data are interpreted by the Fuoss-Kraus theory, yielding values for the ion-pair and triple-ion formation constants. The Raman spectra suggest the presence of "spectroscopically free" ClO4-, BF4-, and AsF6-, ions in solutions, whereas there is no such evidence for either the Cl- or Br- ion, thus substantiating the very high ion-pair formation constants for LiCl and LiBr as obtained from conductance measurements. The observed processes have been interpreted by an Eigen multistep mechanism. Changes in the Raman bands at ca. 867, 1147, 1452, and 2805 cm(-1) suggest that the solvation of Li+ ion in DME occurs through the ethereal oxygen atom of the solvent molecule.