This study presents an in-depth analysis of the physical, optical, electron paramagnetic resonance (EPR), and radiation shielding properties of vanadium-doped cadmium lead borate tellurite glasses, coded as PCTBVX. A series of glasses with varying concentrations of vanadium oxide (V2O5) were synthesized and characterized to understand their structural and functional capabilities. The physical properties, determined through density and molar volume measurements, revealed a notable decrease in density and an increase in molar volume with increasing V2O5 content. This trend was attributed to the substitution of denser CdO with lighter V2O5, and the transformation of BO4 tetrahedra into BO3 triangles in the glass network. X-ray diffraction (XRD) analysis provided insights into the crystalline structures, indicating distinct patterns for each glass composition. Optical properties were investigated using UV–Visible spectroscopy and Tauc plots, revealing a nonlinear decrease in optical band gap energies as V2O5 concentration increased. This observation suggested alterations in the boro-tellurite network structure due to V2O5 addition. EPR spectroscopy was employed to examine the local structures around V4+ ions, demonstrating a correlation between V2O5 concentration and EPR signal strength, indicative of the vanadium ions' coordination environment. The study's highlight was the comprehensive evaluation of radiation shielding properties using Monte Carlo N-Particle Transport Code (MCNP5) simulations and Phy-X/PSD software. These analyses showcased the glasses' capabilities in gamma and neutron attenuation, with a focus on parameters such as attenuation coefficients, effective atomic numbers, and removal cross-sections. The findings revealed that increasing vanadium concentration enhanced the glasses' shielding effectiveness against both gamma and neutron radiation. Overall, the synthesized PCTBVX glasses demonstrated promising attributes for applications in radiation shielding and optical technologies, owing to their modified density, structural alterations, and improved functional properties brought about by vanadium doping. This research not only contributes to the understanding of vanadium's role in glass matrices but also paves the way for developing advanced materials for protective and optical applications.