Di-urea cross-linked POE/siloxane hybrid ormolytes (di-ureasils) doped with a wide concentration range of lithium perchlorate trihydrate (LiClO4·3H2O) (200 ≥ n ≥ 0.5, where n expresses the salt content in terms of the number of ether oxygen atoms per Li+ ion) have been analysed by Fourier transform infrared and Raman (FT-IR and FT-Raman, respectively) spectroscopies and X-ray diffraction (XRD). The results obtained lead us to conclude that the xerogels with n ≥ 5 are totally amorphous. At n ≤ 1 free salt is observed. “Free” ClO4− ions appear to be the main charge carriers at the conductivity maximum located within the 25 ≤ n ≤ 8 composition range of this family of ormolytes. At n = 15 ClO4− ions coordinated in mono/tridentate (C3v symmetry) and bidentate (C2v symmetry) configurations were detected. In salt-rich samples with n