This study aims to investigate the impact of the rare earth element yttrium on the optical properties of chromium (Cr)-doped borate glasses. A series of borate glasses (labeled as BNaCrY glasses) were prepared and studied, each with a constant amount of chromium trioxide (CrO3) but doped with varying amounts of yttrium oxide (Y2O3). Infrared analysis revealed four distinct spectral areas in the internal structure of all BNaCrY glasses. Optical absorption spectra were used to investigate the impact of Y2O3 doping on the optical transitions of BNaCrY glasses. The presence of Cr cations caused the appearance of an absorption band at 379–383 nm, which overlapped with the Urbach edge that is commonly given an edge-like at 430 nm. The Urbach edge has been manifested through a full deconvolution attempt. Cr cations in the Cr3+ state were confirmed by visible absorption bands and are nestled in the octahedral positions. The band at 574–593 nm was used to determine the crystal field splitting (10Dq) for all BNaCrY glasses. Due to the increased number of O anions around the Cr cation, the values of 10Dq increased with Y2O3 doping. The remarkable increase in 10Dq was attributed to increased interaction between Cr cations and their surroundings. In contrast, the shielding parameters were taken into account when evaluating the ability of these transparent glasses to protect against nuclear radiation. We found that the sample with the highest Y2O3 concentration had the highest linear attenuation coefficient and the lowest half-value layer. Thus, BNaCrY glasses are more efficient as attenuators than commercial glasses (such as the Rider and Osmania glasses), especially at low photon energies.