Li8Ge4O12, a ternary electrolyte compound of Li+-based battery, presents the unusual essential properties. The main features are thoroughly explored from the first-principles calculations. The concise pictures, the critical orbital hybridizations in Li-O and Ge-O bonds, are clearly examined through the optimal Moiré superlattice, the atom-dominated electronic energy spectrum, the spatial charge densities, the atom-and orbital-decomposed van Hove singularities, and the strong optical responses. The unusual optical transitions cover the red-shift optical gap, 14 frequency-dependent absorption structures and the most prominent plasmon mode in terms of the dielectric functions, energy loss functions, reflectance spectra, and absorption coefficients. Optical excitations, depending on the directions of electric polarization, are strongly affected by the excitonic effects. The close combinations of electronic and optical properties can identify a significant orbital hybridization for each available excitation channel. The developed theoretical framework will be very useful in fully understanding the diverse phenomena of cathode/electrolyte/anode materials in ion-based batteries.