© 2021, The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.Structural, thermal, radiation shielding efficiency, and buildup factors of the successfully synthesized (100-x) (0.5V2O5–0.5P2O5) (xB2O3): x = 0 (VPB0), 2 (VPB2), 4 (VPB4), 6 (VPB6), 8 (VPB8) mol % glasses have been investigated. Scanning electron microscope (SEM), EDX, Raman spectroscopy, and differential scanning calorimetry (DSC) thermograms measurements of the proposed glasses have been used to perform the mentioned aims. Indeed, radiation protection quantities like linear reduction (μ), and transmission factors (TF), radiation protection efficiency (RPE), and buildup factors (EBF and EABF) have been evaluated via Phy-X/PSD software. The SEM and EDX spectra measurements proved that the structure of the proposed glasses is amorphous. Raman spectroscopy revealed that in VPB8 glass structure, the different phosphate units were formed and thus (PO3)− groups decreased. Thermal stabilities varied between 168 °C (VPB0) and 199 °C (VPB4). The maximum values for the (μ) at 0.015 MeV, where they changed between 45.689 and 42.992 cm−1 for the investigated glasses VPB0–VPB8, respectively, and followed the trend: (μ)VPB0 > (μ)VPB2 > (μ) VPB4 > (μ)VPB6 > (μ)VPB8. The (TF) was linearly increased with the progressing of the photon energy, while the (RPE) has a totally opposite trend with the (TF). The values of the EBF and EABF increased with the increase in the B2O3 substitution ratio, where the lowest and highest buildup factors were obtained at 0 and 8 mol% B2O3 for VPB0 and VPB8, respectively. VPB8 is also found as an effective material to shield the fast neutrons, and its effective removal cross section (ERCSFN) ∑R is found equal 0.0324 (cm2 g−1).