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Base and glass samples with nominal compositions 65B2O3-15NaF-15ZnO-5Bi2O3-0.25CoO-XLa2O3 with X = 0.0–0.6 mol% were produced using the melt quenching technique. The nature of the samples, and the physical, FTIR, and dielectric characteristics were investigated. The XRD data confirmed the non-crystalline state of samples. The density (Ds) of the base and La-X glasses was varied from 3.10 g cm−3 to 3.42 g cm−3. The molar volume (Vm) was decreased from 28.05 cm3/mol to 26.46 cm3/mol. Values of the oxygen molar volume (OMV) declined from 12.47 cm3/mol to 11.83 cm3/mol. The oxygen packing density (OPD) increased from 80.20 g atm l−1 to 84.52 g atm l−1. The FTIR measurements confirmed that incorporation of CoO and La2O3 caused an increased conversion of BO3 to BO4, which caused NBOs to decline and vanish throughout this process. All the glasses under consideration, which were loaded with various quantities of lanthanum (La2O3) and a constant amount of cobalt (CoO), showed a considerable decrease in dielectric constant (ε′) as the frequency rose throughout the low-frequency band. The ε′ decreased dramatically with the addition of CoO. Then, it decreased more when La2O3 was added, achieving 0.4 mol% at the constant amount of CoO. Among the examined samples, the glass sample (La-0.4) loaded with 0.25 mol% of CoO and 0.4 mol% of La2O3 is thought to be promising material for electronic packaging since it has the fastest transmission speed and the lowest dielectric constant. [ABSTRACT FROM AUTHOR]