The synthesis of 25 Li2O – 10 GeO2 – 60 SiO2 – 5 R (R = TeO2, SrO, SeO2, Tl2O, Al2O3) glasses was done by melt quenching technique. X-ray diffraction (XRD) studies confirmed the crystalline phases of synthesized samples after the heat treatment, which is also portrayed in Scanning Electron Microscope (SEM) images. Energy Dispersive Spectroscopy (EDS) depicted the presence of the elements used in the synthesis. Differential Scanning Calorimetry (DSC) curves evidenced ceramic nature of all samples, also their glass-forming ability and thermal stability, which are high for Al-doped sample. X-ray Photoelectron Spectroscopy (XPS) studies revealed the relative increment of BOs in the network of the Al-doped sample. Makishima–Mackenzie model was employed to calculate Young’s modulus, bulk modulus, shear modulus, longitudinal modulus, Poisson’s ratio, microhardness, fractal bond connectivity, average crosslink density, and bond number per unit volume of the samples. These findings indicated the notable mechanical properties of the Al2O3 mixed sample, owing to its large dissociation energy and high field strength. The optical band gap, index of refraction, molar polarizability, molar refractivity, metallization criterion, optical transmission, reflection loss, optical basicity, and electronic polarizability were calculated using the optical absorption studies. Fourier-Transform Infrared Spectroscopy (FTIR) studies of the synthesized samples revealed the presence of SiO4, LiO4, TeO3, TeO4, GeO4, AlO4, and AlO6 structural units in the glass ceramic matrix. From the impedance analysis, it was observed that the ionic conductivity of the glass ceramics containing 5 mol% of Al2O3, Tl2O is minimal (2.06 × 10−6 and 0.44 × 10−6 S/cm at 200 °C respectively) at all temperatures, indicating their suitability for dielectric applications. The maximum ionic conductivity (8.21 × 10−6 S/cm at 200 °C) of the TeO2 doped sample appraises its suitability for solid electrolytic applications.