SiO2–B2O3-GdF3-CaO-Bi2O3 doped glasses containing Er3+/Yb3+ ions at varying concentrations were successfully synthesized using a high-temperature melting method. The glass samples' physicochemical properties and amorphous structure were characterized through density, XRD, XPS, FT-IR, and Raman analyses. Thermal expansion coefficient testing indicated good thermal stability of the glass system. Increasing the Yb3+ doping concentration enhanced near-infrared luminescence at 1.53 μm, with maximum luminescence intensity at approximately 3.2 mol% doping concentration. The energy transfer mechanism of Er3+/Yb3+ doped SiO2–B2O3-GdF3-CaO-Bi2O3 glass was elucidated through fluorescence spectrum analysis, revealing J-O parameters Ω2 = 11.2 × 10−20 cm2, Ω4 = 8.9 × 10−20 cm2, and Ω6 = 9.59 × 10−20 cm2. Calculations for absorption cross-section, cross-section of emission, and gain curve additionally reinforced the glass's capability for laser uses.