A conventional melt-quenching route was employed to elaborate the selected boro-silica-phosphate glasses B2O3-Bi2O3-Si2O-CaO-P2O5. The glassy compositions were chosen to be: 0, 5, 10, and 15 Bi2O3 mol%. The prepared glasses have been subjected to different characterization techniques. Through the substitution of B2O3 with Bi2O3, the glass network's density, molar volume, oxygen molar volume, oxygen packing density (OPD), oxygen/boron ratios, and structural transformations were explored. There was a parallel increase in the density and molar volume from 2.676 ± 0.001 to 2.951 ± 0.001 g/cm3 and from 22.960 to 40.965 cm3/mol, with an increase in the content of Bi2O3 from 0 to 15 mol%. Simultaneously, there was an increase in the oxygen molar volume values from 15.640 to 27.905 cm3/mol, while the OPD values decreased from 63.937 to 35.835 g.atm/L. Infrared spectra analysis showed that the substitution of B2O3 by Bi2O3 led to bridging oxygens' conversion into non-bridging oxygens. The evaluation of these glasses' mechanical properties was done by investigating the following parameters that were altered via Bi2O3 doping: the bulk modulus (K), longitudinal modulus (L), Poisson coefficient, shear modulus (S), and Young's modulus (E). These prepared glasses' radiation-shielding properties were evaluated, with 0.511 MeV reported as the effective atomic number (Zeff). The glass with x = 15% was revealed as having the most elevated Zeff. Zeff was also found to have increased almost two-fold when there was an increase in the Bi2O3 concentration from 0 to 15 mol%.