The structural and electrical properties of vanadium-copper-phosphate glasses with compositions of xV2O5–(40—x)Cu2O–60P2O5 (where x = 10, 20, 30, and 40 mol%) have been thoroughly investigated. As the amount of V2O5 increases, the density falls, and the molar volume rises. This effect may be attributed to the polarizing power strength, which reflects the ratio of the cation's charge to its diameter. As the concentration of V2O5 increases, the DC conductivity shows an upward trend while the activation energy decreases. Additionally, the microstructure—more specifically, the dimensions of vacancy-type defects-studied utilizing using positron annihilation lifetime (PAL) spectroscopy. A correlation was established between the sample characteristics and the PAL results. By computing the distribution of the long lifetime inferred from the PAL, the magnitude of the vacancy-type flaws was verified. The findings offer insightful information about how the PAL and sample characteristics relate to one another.