25Li2O-(10-x)GeO2-60SiO2-5Al2O3-xTiO2 (x = 1–5 mol%) samples namely T1-T5 were produced through the melt quenching method. X-ray Diffraction (XRD) studies recognized the amorphous and crystalline phases of samples. Among T1 to T5 samples, the T3 sample exhibited high glass-forming ability and thermal stability (ΔT = 173 °C), with high crystallization energy (273.89 kJ/mol) and low Avrami index. Mixed electronic-ionic conduction of samples was studied by employing the Small Polaron Hopping (SPH) model. DC ionic conduction of samples was studied by utilizing the Anderson and Stuart model. A novel approach was used to find strain energy in samples using shear moduli from the Makishima-Mackenzie model. The T3 sample had the lowest ionic conductivity (3.86 ×10−9 S/cm at 303 K), highest activation energy (0.808 eV), and exhibited a low (0.50 ×10−15 cm2 V−1 s−1 at 303 K) charge carrier mobility. These findings indicate that the optimized T3 sample is suitable for dielectric applications.