This paper delves into the effect of replacing B2O3 with CuO on the structural, optical absorption, thermal, mechanical, and gamma(γ)-ray shielding properties of four CKB glasses formulated as (65-y)B2O3–15Bi2O3–20K2O-yCuO (where y = 0, 0.3, 0.6, and 1.2 mol%). The glasses were created using the melt-quenching technique, and their non-crystalline structure was verified by X-ray diffraction (XRD) analysis. Fourier-transform infrared (FTIR) spectroscopy identified several structural groups, predominantly consisting of BO3, BO4 units, and B–O–B linkages. Thermal properties, assessed via Differential Scanning Calorimetry (DSC), indicated that the glass transition temperature was highest for the 0.3 mol% CuO sample (CKB0.3), demonstrating enhanced thermal stability in comparison to other compositions. Density measurements correlated positively with CuO concentration, peaking at 1.2 mol%, while molar volume, boron molar volume, oxygen packing density, and boron-boron separation distances showed a decreasing trend with increased CuO concentration. UV–Vis absorption spectroscopy indicated a decline in the optical energy gap and an increase in Urbach energy, attributed to the conversion of BO3 into BO4 units in the glass matrix. Mechanical properties, evaluated using the Makishima-Mackenzie model, demonstrated enhancements in elastic moduli and micro-hardness with rising CuO concentration. The γ-ray shielding properties (γ-RPs) were examined at energies of 0.662, 1.173, and 1.333 MeV, revealing that both the linear attenuation coefficient and effective atomic number reached their maximum values at 1.2 mol% CuO (CKB1.2). While CKB1.2 exhibited excellent mechanical and γ-ray shielding performance, CKB0.3 excelled in thermal stability and demonstrated γ-ray shielding efficiency comparable to CKB1.2. This suggests that CKB0.3 is a promising candidate for radiation shielding applications requiring a balanced combination of thermal stability and effective γ-ray attenuation properties, particularly at 0.662 MeV.