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Abstract The multi-component glass system has a composition of 10K2O–10ZnO–55 B2O3–(25–x)V2O5–xBi2O3 (x = 4, 5, 7.5, 9, 10 mol%) are synthesized by the melt-quenching method. Using X-ray diffraction examination, the amorphous phase in the material was confirmed. The physical characteristics of the produced compositions are examined using density (D) and molar volume (Vm). Calculations of physical properties showed that adding Bi2O3 from 4 to 10 mol% increased the glass density from 2.7878 to 3.3617 g cm−3 and decreased the molar volume from 40.4196 to 38.5895 cm3/mol. Studies of glass samples using the FTIR show bands of absorption for oxides in different structural groups. Octahedral [ $${{\text{BiO}}}_{6}$$ BiO 6 ], [ $${{\text{BO}}}_{4}$$ BO 4 ], and tetrahedral [ $${{\text{BO}}}_{3}$$ BO 3 ] structural units are observed in the present glass matrices. The cutoff wavelength ( $${\lambda }_{C}$$ λ C ), and optical band gap energy were determined using UV absorption spectra. The increase in non-bridging oxygens can be linked to the decrease in optical band gap energy ( $${E}_{opt}$$ E opt ) (direct and indirect) and the increase in cutoff wavelength with an increase in Bi2O3 content. This is attributed to the existence of bismuth ions and the creation of non-bridging oxygens. Besides that, the values of optical parameters, viz., optical electronegativity, refractive index, and molar refractivity, are calculated. The metallization criterion values are less than 1 and the glass samples exhibit an increased tendency towards metallization. Both the conductivity and the dielectric constant increase with the rise in Bi2O3 content, however, the dielectric loss and the impedance reduce. The behavior and values of conductivity for the studied glasses reveal the semiconducting properties of all glass samples. These results suggest that the produced glass samples may be employed as amorphous semiconductors in electronics and memory switching devices.