Changes in glass transition and ionic association of PPG/LiClO4 samples with increasing salt concentration have been studied using temperature modulated differential scanning calorimetry (TMDSC)and micro Raman spectroscopy, respectively. PPG, of average molar mass of 3000, was used as host for LiClO4 over the range O:Li = 35 – 4. The analysis of the Raman band, obtained at room temperature, associated with the ν1 symmetric stretching mode of ClO4 - anions, shows the presence of ionic association (ion pair) for electrolytes with salt concentration higher than O:Li = 8. The glass transition changes in the electrolytes were investigated using the differential of heat capacity with respect to temperature [dCp/dT], obtained from TMDSC. The analysis of the dCp/dT signal, by fitting with Gaussian curves, showed that there is a glass transition splitting in samples with concentrations higher than O:Li = 16, which indicates the presence of nanoheterogeneities in these amorphous electrolytes. Raman results pemit to affirm that this nanoheterogeneities were associated mainly with solvent separated ion pairs regions of different concentrations, and not with aggregate of ionic species.