The current paper investigates the impact of silver iodide (AgI) on the structure, optical, and radiation shielding parameters of borate glasses embedded with low amounts of CrO3, high levels of Na2O, and various quantities of AgI (from 1 to 5 mol%). These glasses (named BNaCrAg-glasses) were synthesized and their properties were investigated. Fourier transform infrared (FTIR) analyses of BNaCrAg-glasses demonstrated that the ratio of BO4/BO3 units increased with increasing AgI. The existence of Cr cations, with their Cr6+ state, was recognized from the absorption bands at 384–392 nm and 334–338 nm. Furthermore, the absorption bands at 580–589 nm at 409–440 nm through the visible region confirmed the existence of Cr-ions as Cr3+ in the octahedral symmetry. The crystal field splitting (10Dq) was calculated from the 580–589 nm bands. The values of 10Dq decreased with AgI doping due to replacing oxygen with iodide anions. The transmittance at 700 nm increased from 24 to 80%, while AgI addition increased from 0 to 5 mol%. The glass sample with the highest AgI content had the lowest half-value layer and maximum linear attenuation coefficient. Thus, the new BNaCrAg-glasses combine good transparency with good attenuation of low energy radiation and can be used to protect the radiation workers. Furthermore, these glasses offer high-energy optical transitions suitable for UV optics, such as ultraviolet digital photography and insect light traps.