Novel transparent glasses with nominal composition of 50B2O3 +15Na2O+15ZnO+(20−x)CaO+xBi2O3; x = 0, 5, 10, 15, and 20 were synthesized using melt quenching method. The molar volume and density of the produced glasses with boosting the substitution ratio of Bi2O3 were measured. X-ray diffraction (XRD) patterns of the glasses were obtained for confirming their amorphous structure. UV–Vis spectra of the prepared samples were detected over the range of 190–1100 nm. By using UV–Vis results, Fermi level energy (Ef), refractive index (n), optical energy gap (Eg), Urbach's energy (Eu), and optical dispersion parameters were estimated. Results exposed that the optical energy gap (Eg) and single-oscillator energy (Eo) were decreased however other parameters increased with increasing Bi2O3 content. Mass attenuation coefficient (μ/ρ), as an essential variable for photon protecting research, was attained at 0.015–15 MeV photon energies for investigated glasses. Other relevant variables that can define the photon protecting features like Mean Free Path (MFP), Half Value Layer (HVL), equivalent atomic number (Zeq), gamma-ray exposure buildup factor (EBF), energy-absorption buildup factor (EABF) were obtained for the prepared glasses. The corollaries revealed that the BCNZB20.0 glass can be a strong shield material against gamma radiation. Finally, the proficiency of proposed glasses to stop fast neutrons charged alpha and proton particles was explored utilizing effective removal cross section (ΣR) and Mass Stopping Power (MSP) parameters. The glass with 20% Bi2O3 (BCNZB20.0) addition is very effective in preventing charged and uncharged particles. The addition of Bi2O3 to the studied glass system not only improved the optical and structural features but also the nuclear radiation shielding properties.