The present study has been focused on environmentally friendly sol–gel-derived electrolytes based on a di-urethane cross-linked d-PCL(530)/siloxane network [where d represents di, PCL identifies the poly(ε-caprolactone) biopolymer, and 530 is the average molecular weight in grams per mole] doped with a wide range of concentration of lithium perchlorate and lithium bis(trifluoromethanesulfonyl)imide. Fourier Transform Infrared and Raman spectroscopies have been applied to evaluate the extent of ionic association. Characteristic bands of the PCL(530) segments, of the urethane cross-links, and of the anions have been examined to gain insight into the cation/biopolymer, cation/anion, and cation/cross-link interactions. In both electrolyte systems, “free” ions and contact ions have been identified. The addition of salt modifies the hydrogen-bonded array of the host matrix, causing the destruction/formation of the urethane/urethane aggregates.